A novel method of photoinduced synthesis of unsymmetrical diaryl selenides from triarylbismuthines and diaryldiselenides has been developed. Although the arylation reactions with triarylbismuthines are usually catalyzed by transition-metal complexes, the present arylation of diaryldiselenides with triarylbismuthines proceeds upon photoirradiation in the absence of transition-metal catalysts. A variety