Four air-stable hypervalent organobismuth compounds with (C,O)- or (C,S)-chelating ligands, namely, R2BiCl (R=2-(MeECH 2)C6H4; E=O (3), S (4)), [2-(MeOCH 2)C6H4]2BiOTf (5), and [{2-(MeSCH2)C6H4}2Bi][OTf] (6; OTf=triflate) were successfully synthesized. The structures of compounds 3-6 were determined by single-crystal X-ray diffraction. Compound 6 comprises the [2-(MeSCH2)C6H4]2Bi+ cation and the OTf- anion. Compounds 5 exhibited good catalytic efficiency and reusability for the allylation reaction of different aldehydes with tetraallyltin in me...