A novel coupling reaction of diaryl methanols with ketones or aldehydes has been developed under the catalysis of AlCl3. Various ketones and aldehydes could couple with 9H‐xanthen‐9‐ol smoothly, affording coupling products in 48% –88% yields. A plausible mechanism using AlCl3 to activate both diaryl methanol and ketone or aldehyde is proposed.