Orthorhombic Bi2S3 (bismuthinite) nanorods and nanowires were synthesized by the solventless thermolysis of bismuth alkylthiolate precursors. Reactions producing high aspect ratio nanowires were carried out in air at 225°C with the presence of a capping ligand species, octanoate. Nanorods with a lower aspect ratio were produced by the same approach with the addition of elemental sulfur at a lower temperature (~160°C). Current density –Voltage characterization of the devices under illumination with 500 W Xenon lamp showed the photovoltaic performance. Both the nanorods and the nanowires hybrid with the polymer show the improved photovoltaic performance than polymer only. As far as we know, we are the first to apply Bi2S3 nanorods and nanowires to solar cells with the structure of ITO/PEDOT:PSS/MDMO-PPV:Bi2S3/Al.