When the pitcher: 1.switches his pitching stance from the windup position to the set position (or vice versa) without properly disengaging the rubber; 2. when going from the stretch to the set position, fails to make a complete stop with his hands together before beginning to pitch; 3. throws from the rubber to a base without stepping toward (gaining distance in the direction of) that base; 4. throws from the rubber to a base where there is no runner and no possibility of a play; 5. steps or feints from the rubber to first base without completing the throw; 6. pitches a quick return pitch, that is, pitches with the intent to catch the batter off-guard; 7. pitches or mimics a part of his pitching motion while not in contact with the rubber; 8. drops the ball while on the rubber; 9. after a feint or throw to a base from the rubber, fails to disengage the rubber before reengaging and pitching; 10. after beginning to pitch, interrupts his pitching motion; 11. begins to pitch while the catcher is out of the catcher's box when giving an intentional walk; 12. while pitching, removes his pivot foot from the pitching rubber, except to pivot or as a natural consequence of stepping forward to release the pitch inordinately delays the game; 13. pitches while facing away from the batter; 14. after bringing his hands together on the rubber, separates them except in making a pitch or a throw; or stands on or astride the rubber without the ball, or mimics a pitch without the ball In addition, if a pitcher commits any of the following illegal actions, it may result in a balk under certain circumstances: expectorates on the ball, either hand or his glove; rubs the ball on his glove, person or clothing; applies a foreign substance of any kind to the ball; deface the ball in any manner; or delivers a ball altered in a manner described above or what is called the “shine” ball, “spit” ball, “mud” ball or “emery” ball.
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That is a difficult question to answer since game stats and play-by-play logs can be very difficult to find for games played many, many years ago. That said, since 1965 there have been 14 MLB games that ended on a walk-off balk ...
1) April 28, 1965 - Cubs pitcher Ernie Broglio balked in the winning run in the bottom of the 14th inning giving the Reds a 3-2 win.
2) June 8, 1965 - Astros pitcher Hal Woodeshick balked in the winning run in the bottom of the 11th inning giving the Pirates a 7-6 win.
3) Aptil 29, 1973 - Expos pitcher Tom Walker balked in the winning run in the bottom of the 9th inning giving the Astros a 4-3 win.
4) September 29, 1978 - Phillies pitcher Warren Brusster balked in the winning run in the bottom of the 9th inning giving the Pirates a 2-1 win.
5) July 10, 1986 - Angels pitcher Todd Fischer balked in the winning run in the bottom of the 12th inning giving the Red Sox an 8-7 win.
6) May 28, 1989 - Mets pitcher Roger McDowell balked in the winning run in the bottom of the 12th inning to give the Dodgers a 4-3 win.
7) July 4, 1993 - Marlins pitcher Matt Turner balked in the winning run in the bottom of the 9th inning giving the Braves a 4-3 win.
8) April 28, 2000 - Rangers pitcher Jeff Zimmerman balked in the winning run in the bottom of the 9th inning giving the Orioles a 4-3 win.
9) May 8, 2000 - Braves pitcher John Rocker balked in the winning run in the bottom of the 9th inning giving the Marlins a 3-2 win.
10) April 19, 2004 - Athletics pitcher Justin Duchscherer balked in the winning run in the bottom of the 14th inning giving the Mariners a 2-1 win.
11) July 15, 2005 - Nationals pitcher Mike Stanton balked in the winning run in the bottom of the 10th inning giving the Brewers a 4-3 win.
12) September 9, 2008 - Rockies pitcher Taylor Buchholz balked in the winning run in the bottom of the 10th inning giving the Braves a 5-4 win.
13) May 31, 2010 - Diamondbacks pitcher Esmerling Vasquez balked in the winning run in the bottom of the 9th inning giving the Dodgers a 5-4 win.
14) June 16, 2011 - Mets pitcher D.J. Carrasco balked in the winning run in the bottom of the 10th inning giving the Braves a 9-8 win.
No, any actions that would be considered a balk with men on base would be called a ball with the bases empty.