Petway played for the Cuban X-Giants (1906), LeLand Giants (1906-10), Brooklyn Royal Giants & Phila. Giants (1908-09), Chicago American Giants (1911-18), and the Detroit Stars (1919-25).
Petway dropped his pursuit of a career in medicine at Nashville's Meharry Medical College in 1906 to play pro baseball.
He quickly became known as one of the best black catchers; he proved himself in a series against the Detroit Tigers played in Cuba in 1910 in which he batted .390 and threw Ty Cobb out at three times on three attempts.
He is reported to have been the first catcher to consistently throw to second base without rising from the squat.