In summary, we have developed a straightforward and programmable protocol for the direct selective synthesis of a diverse range of unsymmetrical diarylmethanes and diarylketone, structural motifs found in many important chemicals. These protocols involve a site-selective one-pot, four-component coupling reaction of commercially available aldehydes and arenes with Ph₃P and TfOH, yielding benzhydryl triarylphosphonium salts.