We report the effect of NaF precursors on the preferential orientation of Cu(In,Ga)Se2 (CIGS) thin films. The CIGS films were grown on NaF/Mo/glass and Mo/glass substrates by using a multi-stage co-evaporation method. The 23-nm-thick NaF precursors were prepared by using an evaporation technique. The CIGS film with a NaF precursor shows a much higher I(112)/I(220/204) XRD peak intensity ratio than the film without it. The (112)- and (220/204)-oriented CIGS films were obtained from highly (0006)- and (30–30)-oriented (In,Ga)2Se3 (IGS) films, respectively. The IGS (0006) orientation was enhanced by the NaF precursor because the lattice misfit of IGS (0006) plane on NaF (−2.3%) was lower than that of IGS (0006) plane on Mo (5.1%) whereas the lattice misfit of IGS (30–30) plane on NaF (1.3%) was higher than that of IGS (30–30) plane on Mo (0.1%). The degree of lattice misfit is believed to play an important role in the preferential growth of CIGS films in the (112) orientation.