In this study, photoluminescence (PL) measurements were used to characterized Cu(In,Ga)Se2 nanotip arrays (CIGS NTRs). Large area CIGS NTRs were yielded by using one step Ar+ milling process without template. Formation mechanism of NTRs is due to a highly anisotropic milling effect of the quaternary components compound. In both CIGS thin films with and without NTRs, saturation effects of Donor-Acceptor Pair (DAP) had been observed while excitation power dependence PL measurements. Comparing with thin film CIGS without NTRs, it has revealed that the concentration DAP had been changed after formation of CIGS NTRs and had enhanced its carrier density of the p-type semiconductor.