Mo-based thin films are frequently used as back electrode materials because of their low resistivity and high crystallinity in CIGS chalcopyrite solar cells. Mo:Na/Mo bilayer thin films with 1 μm thickness were deposited on soda lime glass by varying the thickness of each layer using dc-magnetron sputtering. The effects of the Mo:Na layer on morphology and electrical property in terms of resistivity were systematically investigated. The resistivity increased from 159 μΩ·cm to 944 μΩ·cm; this seemed to be caused by increased surface defects and low crystallinity as the thickness of Mo:Na layer increased from 100 nm to 500 nm. The surface morphologies of the Mo thin films changed from a somewhat coarse fibrous structures to irregular and fine celled structures with increased surface cracks along the cell boundaries as the thickness of Mo:Na layer increased. Na contents varied drastically from 0.03 % to 0.52 % according to the variation of Mo:Na layer thickness. The change in Na content may be ascribed to changes in surface morphology and crystallinity of the thin films.