CuInSe2 (CIS) films on Mo/soda-lime glass were prepared by selenization of sputtered precursors from Cu2Se and In2Se3 binary targets. Cu–In–Se precursors were sequentially sputtered with double-layered structure of both Cu2Se/In2Se3 and In2Se3/Cu2Se. The structural, compositional and electrical properties of annealed Cu–In–Se precursors were investigated for solar cell applications. Better adhesion between CIS and Mo back contact was observed in the double-layered structure of Cu2Se/In2Se3 at all working pressures. Less MoSe2 phase on both structures was generated at a lower working pressure of 0.67Pa. A CIS solar cell with Al/Al-doped ZnO/i-ZnO/CdS/CIS (900nm, Cu2Se/In2Se3 at 0.67Pa)/Mo/soda-lime glass was continuously fabricated, and its conversion efficiency was 4.6%, with 346mV of open circuit voltage, 30.5mA/cm2 of short circuit current density and 43.5% fill factor.