We report a simple solvothermal synthesis approach to the growth of CuInS2 nanocrystals with zincblende- and wurtzite-phase structures. Zincblende nanocrystals with particle sizes of 10-20 nm were produced using oleylamine as the solvent. When ethylenediamine was used as the solvent, similarly sized wurtzite nanocrystals with some degree of particle aggregation were formed. Use of a mixture of these solvents gave products with mixed phases including some polyhedral nanostructures. The crystal phases of these nanocrystals were carefully determined by X-ray diffraction and transmission electron microscopy analysis. All the samples exhibit strong absorption from the entire visible light region to the near-infrared region beyond 1300 nm. Pure-phase zincblende and wurtzite CuInS2 nanocrystals were employed as ink in the fabrication of solar cells. The spray-coated nanocrystal layer was subjected to a selenization process. A power conversion efficiency of similar to 0.74% and a good external quantum efficiency profile over broad wavelengths have been measured. The results demonstrate that wurtzite and zincblende CuInS2 nanocrystals may be attractive precursors to light-absorbing materials for making efficient photovoltaic devices.