The detailed molecular mechanism proposed for the MAO-catalyzed oxidation of amines has been controversial with the basic assumption that both MAO A and MAO B follow the same pathway for the C-H bond cleavage step. Using the mechanistic approach of investigation of electronic effects of various benzylamine ring substituents in experiments at pH 9.0, human MAO A exhibits a kinetic behavior characteristic of an H(+) abstraction, while human MAO B exhibits kinetic properties characteristic of a H(-) abstraction. These results lead to the conclusion that the assumption that MAO A and MAO B follow identical mechanisms is incorrect.