Quantized semiconductor nanoclusters of Bi2S3 are prepared in acetonitrile by reacting BiI3 with H2S or Na2S. Both preparation methods yield stable colloids with particle diameters of less than or equal to 5 nm. Excitation with a 355-nm laser pulse results in transient bleaching in the 400-500-nm region. This process is followed by the formation of S-surf(-) with a difference absorption maximum around 540 nm. This we attribute to the chemical changes associated with the hole-trapping process. A composite thin film electrode comprised of SnO2/Bi2S3 nanocrystallites has been prepared by sequential deposition of SnO2 and Bi2S3 films onto an optically transparent electrode, and its photoelectrochemical behavior has been studied. The thin film is photoactive in the visible and near-IR and exhibits an incident photon to photocurrent efficiency (IPCE) of similar to 15% at 400 nm.