In the present work we have studied the effect of Na on the properties of graded Cu(In1−xGax)Se2 (CIGS) layer. Graded CIGS structures were prepared by chemical spray pyrolysis at a substrate temperature of 350°C on soda lime glass. Sodium chloride is used as a dopant along with metal (Cu/In/Ga) chlorides and n, n-dimethyl selenourea precursors. The addition of Na exhibited better crystallinity with chalcopyrite phase and an improvement in preferential orientation along the (112) plane. Energy dispersive analysis of X-rays (line/point mapping) revealed a graded nature of the film and percentage incorporation of Na (0.86at%). Raman studies showed that the film without sodium doping consists of mixed phase of chalcopyrite and CuAu ordering. Influence of sodium showed a remarkable decrease in electrical resistivity (0.49–0.087Ωcm) as well as an increase in carrier concentration (3.0×1018–2.5×1019cm−3) compared to the un-doped films. As carrier concentration increased after sodium doping, the band gap shifted from 1.32eV to 1.20eV. Activation energies for un-doped and Na doped films from modified Arrhenius plot were calculated to be 0.49eV and 0.20eV, respectively. Extremely short carrier lifetimes in the CIGS thin films were measured by a novel, non-destructive, noncontact method (transmission modulated photoconductive decay). Minority carrier lifetimes of graded CIGS layers without and with external Na doping are found to be 3.0 and 5.6ns, respectively.