Benzene fused 5-membered dichalcogenaheterocycles containing sulfur, selenium, and phosphorus, 2-phenyl-1,3,2-benzodichalcogenaphospholes (4), were newly prepared by the reactions of corresponding 2,2-dimethyl-1,3,2-benzodichalcogenastannoles (3) with dichlorophenylphosphine in excellent yields. The structure of these new 5-membered heterocycles containing tin, phosphorus, sulfur, and selenium was characterized by multi-nuclear nmr experiments.