A synthesis approach for shape control of single crystalline Bi nanostructures has been developed. By controlling the molar ratio of PVP and Bi in a polyol process, Bi nanocubes with an edge length of approximately 60-80 nm, triangular nanoplates with an edge length of 200-500 nm, and nanospheres with an average diameter of 75 nm have been successfully synthesized. In the same synthetic process, Bi nanobelts with lengths of up to 80 microm and widths of up to 0.6 microm were synthesized in large quantities by introducing a trace amount of Fe3+ species into the reaction system. These single crystalline nanostructure Bi materials are expected to find potential applications in a variety of areas including high efficiency thermoelectric devices.