The electrical properties of Cu(In,Ga)Se sub(2)/Mo junctions were characterized with respect of MoSe sub(2) orientation and Na doping level using an inverse transmission line method, in which the Cu(In,Ga)Se sub(2) (CIGS)/Mo contact resistance could be measured separately from the CIGS film sheet resistance. The MoSe sub(2) orientation was controlled by varying the Mo surface density, with the c-axis parallel and normal orientations favored on Mo surfaces of lower and higher density, respectively. The effect of Na doping was compared by using samples with and without a SiO sub(x) film on sodalime glass. The conversion of the MoSe sub(2) orientation from c-axis normal to parallel produced a twofold reduction in CIGS/Mo contact resistance. Measurements of the contact resistances as a function of temperature showed that the difference in CIGS/Mo contact resistance between the samples with different MoSe sub(2) orientations was due to different barrier heights at the back contact. Comparison between Na-doped and Na-reduced samples revealed that the contact resistance for the Na-reduced system was four times of that of the doped sample, which showed more pronounced Schottky-junction behavior at lower temperature, indicating that Na doping effectively reduced the barrier height at the back contact. Copyright copyright 2013 John Wiley & Sons, Ltd. The electrical properties of Cu(In,Ga)Se2/Mo junctions were successfully characterized in terms of contact resistance using modified (inverse) transmission line method, in which the Cu(In,Ga)Se2/Mo contact resistance could be measured separately from the CIGS film sheet resistance. The measurement showed that the substantial Na doping as well as the switching of MoSe2 structure toward c-axis parallel orientation could reduce the barrier height at back contact, favoring higher photovoltaic conversion efficiency.