Molybdenum (Mo) thin films, most commonly used as electrical back contacts in Cu(In,Ga)Se2 (CIGS) solar cells, are deposited by rf and dc magnetron sputtering in identical systems to study the discrepancy and growth mechanisms of the two sputtering techniques. The results reveal that though different techniques generally deposit films with different characteristic properties, Mo films with similar structural and physical properties can be obtained at respective suitable deposition conditions. Highly adhesive and conductive Mo films on soda lime glass are further optimized, and the as-fabricated solar cells reach efficiencies as high as 9.4% and 9.1% without an antireflective layer.