While looking through the stories that happened this day in history, I came upon this item:
1994 - With only 115 fans in attendance on a cold and rainy night at Pohlman Field, Kelly Wunsch becomes the third player and first starting pitcher to strikeout five batters in one inning in professional baseball. The Beloit Brewer hurler, who was drafted by Milwaukee in the first round (26th pick overall) of the 1993 amateur draft, makes this possible when two of those victims reached first base on wild pitches during 7-3 loss to Springfield (IL) of the Midwest League.
I then started searching the other two who struck out five in one inning and I stumbled upon this in the "Strikeout" page on Wikipedia:If a third strike is not caught by the catcher (and is not tipped), it is a strikeout, and the at-bat is over. However, with first base open or with two outs, the batter is not out until tagged out or forced out. On a wild pitch or passed ball the batter can often advance to first base safely. If a runner is at first base and there are less than two outs, the batter is automatically out, as with the infield fly rule. If there are two outs, another runner may be forced out as with any other ball in play. If the runner reaches first base safely, there is no out, but the pitcher is still credited with a strikeout.
It is thus possible for a pitcher to throw four (or more) strikeouts in an inning. The first major leaguer to be credited with the feat was Jon Andre of the New York Giants on October 4, 1888. The feat was once rare, occurring only five times before 1956, but is now so common that it happened six times in 1999. Chuck Finley did it on May 12 and August 15, 1999 with the Anaheim Angels, and then for a third time on April 16, 2000 with the Cleveland Indians. Finley is the only player to pitch four strikeouts in an inning more than once. Kerry Wood of the Chicago Cubs struck out 4 in an inning in 2002, but in his case, 2 batters reached base due to passed balls by his catcher Todd Hundley.[3] This recent increase in the occurrence of the four-strikeout inning may well be credited to the increase in usage of the split-finger fastball and forkball, both pitches that end up in the dirt at the plate when effective and often are difficult to handle for catchers.
With any runners advancing to leave first base open if there are less than two outs, the process can repeat, leading to a fifth strikeout (or more) in the inning. A fifth strikeout has not happened in a regulation game in the major leagues, but has occurred three times in the minor leagues, most recently by Mike Schultz of the Lancaster JetHawks against the Rancho Cucamonga Quakes on July 16, 2004. In the major leagues, knuckleballer Joe Niekro also struck out five men in an inning during a spring exhibition game when Niekro was with the Houston Astros.
It is thus possible for a pitcher to throw four (or more) strikeouts in an inning. The first major leaguer to be credited with the feat was Jon Andre of the New York Giants on October 4, 1888. The feat was once rare, occurring only five times before 1956, but is now so common that it happened six times in 1999. Chuck Finley did it on May 12 and August 15, 1999 with the Anaheim Angels, and then for a third time on April 16, 2000 with the Cleveland Indians. Finley is the only player to pitch four strikeouts in an inning more than once. Kerry Wood of the Chicago Cubs struck out 4 in an inning in 2002, but in his case, 2 batters reached base due to passed balls by his catcher Todd Hundley.[3] This recent increase in the occurrence of the four-strikeout inning may well be credited to the increase in usage of the split-finger fastball and forkball, both pitches that end up in the dirt at the plate when effective and often are difficult to handle for catchers.
With any runners advancing to leave first base open if there are less than two outs, the process can repeat, leading to a fifth strikeout (or more) in the inning. A fifth strikeout has not happened in a regulation game in the major leagues, but has occurred three times in the minor leagues, most recently by Mike Schultz of the Lancaster JetHawks against the Rancho Cucamonga Quakes on July 16, 2004. In the major leagues, knuckleballer Joe Niekro also struck out five men in an inning during a spring exhibition game when Niekro was with the Houston Astros.

Right on the sweet spot (calpounder/flickr)
You can read about the Mike Schultz feat here.
Baseball Almanac presents all pitchers who've struck out four batters in one inning and also have this tidbit at the bottom of the page:
In the American League, the following pitchers struck out all four (4) batters in consecutive order: Mike Cuellar, Mike Paxton, Bobby Witt, Kevin Appier, Wilson Alvarez, Chuck Finley and Kazuhiro Sasaki.
In the National League, the following pitchers struck out all four (4) batters in consecutive order: Ed Crane, Hooks Wiltse, Jim Davis, Pete Richert, Don Drysdale, Bill Bonham, Kirt Ojala, Steve Kline and Octavio Dotel.
On September 30, 1885, Bobby Mathews became the first and only pitcher in the American Association to accomplish this unique feat. During the 1908 World Series, Orval Overall became the first and only pitcher to accomplish the feat in a Fall Classic.
They also have a great page with many strikeouts feat, check it out.In the National League, the following pitchers struck out all four (4) batters in consecutive order: Ed Crane, Hooks Wiltse, Jim Davis, Pete Richert, Don Drysdale, Bill Bonham, Kirt Ojala, Steve Kline and Octavio Dotel.
On September 30, 1885, Bobby Mathews became the first and only pitcher in the American Association to accomplish this unique feat. During the 1908 World Series, Orval Overall became the first and only pitcher to accomplish the feat in a Fall Classic.

