In this paper, we examine photoluminescence spectra of Cu(In,Ga)Se(2) (CIGS) via temperature-dependent and power-dependent photoluminescence (PL). Donor-acceptor pair (DAP) transition, near-band-edge transition were identified by their activation energies. S-shaped displacement of peak position was observed and was attributed to carrier confinement caused by potential fluctuation. This coincides well with the obtained activation energy at low temperature. We also present a model for transition from V(Se) to V(In) and to V(Cu) which illustrates competing mechanisms between DAPs recombinations.