Colloidal quantum dots (QDs) have attracted a great amount of attention for their appealing optoelectronic properties. In this work, the CuInS2 (CIS)/ZnS core/shell QDs based on 4.3 nm cores with various layers of ZnS shell (0 to 10) were synthesized. With the sequential growth of a ZnS shell over a CIS core, the band alignment of core/shell QDs converts from a type I to quasi-type II structure. This conversion prolongs the carrier lifetime and affects the electron transfer rate (K-et) and electron transfer efficiency (eta(ET)) A comparative study indicates that the photovoltaic performance of CIS based QDSCs can be markedly improved by optimizing the layers of ZnS shell. The highest photo conversion efficiency (PCE) of 2.07% is obtained at optimum ZnS thickness of about 1.55 nm. These results show tuning the thickness of shell to change the band alignment is an effective strategy to manipulate the carriers transportation behaviors and thus affect the PCE of CIS-based optoelectronic devices. (C) 2019 Elsevier Inc. All rights reserved.