A highly efficient and general nucleophilic substitution reaction between dialkyl H-phosphonates or diarylphosphine oxides and triarylmethanols catalyzed by HOTf (trifluoromethanesulfonic acid) has been developed. It provides an atom-economical protocol for the synthesis of various symmetrical and unsymmetrical phosphorus-substituted triarylmethanes that constitute an emerging family of potent anticancer agents in rich diversity with 40 to 96% yields. The synthetic applicability of this protocol is demonstrated by gram-scale preparations.