Positron annihilation spectroscopy has been used to investigate CuInSe2 solar cell thin films. The films were grown on Mo-coated soda lime glass substrates by the electrochemical deposition processing technique. As-grown samples are found to contain large concentration of vacancy defects. The selenium (Se) atmosphere and sulfur (S) atmosphere annealing of as-grown samples at 800 K can dramatically reduce the number of vacancy defects and the film becomes crystalline. In addition, a defect layer of about 50 nm thickness was observed at the surface of the CuInSe2 thin film. This layer results from the electrochemical deposition method, but the defect concentration in the defect layer can be greatly reduced by annealing in selenium atmosphere. The Doppler broadening line shape parameter correlation plot provided evidence that the positron trapping defect states where in three samples. Crown Copyright (C) 2012 Published by Elsevier B.V. All rights reserved.