The carriers’ behavior in neutral region (NTR) and space charged region (SCR) of Cu(In,Ga)Se2 thin film based solar cells has been investigated by temperature dependent photoluminescence (PL-T), electroluminescence (EL-T) and current-voltage (IV-T) from 10 to 300 K. PL-T spectra show that three kinds of defects, namely VSe, InCu and (InCu+VCu), are localized within the band gap of NTR and SCR of CIGS layer, corresponding to the energy levels of EC-0.08, EC-0.20 and EC-0.25 eV, respectively. The InCu and (InCu+VCu) deep level defects are non-radiative recombination centers at room temperature. The IV-T and EL-T analysis reveals that the injection modes of electrons from ZnO conduction band into Cu(In,Ga)Se2 layer are tunneling, thermally-excited tunneling and thermionic emission under 10-40, 60-160, and 180-300 K, respectively. At 10-160 K, the electrons tunnel into (InCu+VCu) and Vse defect levels in band gap of SCR and the drifting is involved in the emission bands at 0.96 and 1.07 eV, which is the direct evidence for a tunneling assisted recombination. At 180-300 K, the electrons are directly injected into the Cu(In,Ga)Se2 conduction band, and the emission of 1.13 eV are ascribed to the transitions from the conduction band to the valence band.