Hollow CuInS2 microspheres with hierarchical structures were synthesized via solution-based method. The detailed HRTEM and XRD results demonstrated the presence of zincblende CuInS2 microspheres trunks and wurtzite nanobelts attached onto the microspheres. As it was found, oxygen had decisive effect on the formation of CuInS2 microspheres. Detailed investigation indicated the growth of hierarchical structured CuInS2 microspheres simultaneously underwent two different mechanisms, phase transformation for zincblende CuInS2 microspheres and catalytic growth for wurtzite CuInS2 nanobelts. (C) 2014 Elsevier B.V. All rights reserved.