The metal-organic compounds, Bi[(EPR 2 ) 2 N] 3 (E ) S, Se; R ) Ph, i Pr), have been synthesized and used as single-source precursors for the deposition of bismuth chalcogenide thin films via low-pressure and aerosol-assisted metal-organic chemical vapor deposition. Crystalline thin films of rhombohedral Bi 2 Se 3 (using Bi[(SeP i Pr 2 ) 2 N] 3 ), hexagonal BiSe (using Bi[(SePPh 2 ) 2 N] 3 ), and orthorhombic Bi 2 S 3 (using Bi[(SPR 2 ) 2 N] 3 ) have been deposited on glass substrates. Films have been characterized by X-ray powder diffraction, scanning electron microscopy, and energy-dispersive analysis of X-rays.