The Baeyer-Villiger (BV) reaction of acetophenones R-COCH3 (R = phenyl, 4-methylphenyl, 3,4-dimethoxyphenyl) with performic acid (PFA) in formic acid (FA) as the catalyst and solvent was reinvestigated using the MPWB1K functional in conjunction with the 6-311G(d,p) and 6-311++G(d,p) basis sets. For the acid-catalyzed addition step, we used the eight-membered ring transition structure proposed in our previous work. The calculated and experimental results obtained for the BV reaction under the mentioned conditions lead to the conclusion that our mechanism is more reliable than the one reported by Liu and co-workers, in which the acid-catalyzed first step involves a transition state with a six-membered ring structure.