Trifluoromethanesulfonic acid (TfOH) is one of the superior catalysts for acylation. The catalytic activity of TfOH in C-and/or O-acylation has broadened the use of various substrates under mild and neat or forced conditions. In this review, the salient catalytic features of TfOH are summarized, and the unique controllability of its catalytic activity in the tendency of C-acylation and/or O-acylation is discussed.