This paper investigates the electrical properties of electron reflector layer to survey materials as an electron reflector (ER) for chalcopyrite CuInGaSe solar cells. The purpose is optimizing the conduction-band and valence-band offsets at ER layer/CIGS junction that can effectively reduce the electron recombination near the back contact. In this work, an initial device model based on an experimental solar cell is established, then the properties of a solar cell with electron reflector layer are physically analyzed. The electron reflector layer numerically applied to baseline model of thin-film CIGS cell fabricated by ZSW (efficiency = 20.3%). The improvement of efficiency is achievable by electron reflector layer materials with Eg > 1.3 eV and −0.3 < Δχ < 0.7, depends on bandgap. Our simulations examine various electron reflector layer materials and conclude the most suitable electron reflector layer for this real CIGS solar cells. ZnSnP2, CdSiAs2, GaAs, CdTe, Cu2ZnSnS4, InP, CuO, Pb10Ag3Sb11S28, CuIn5S8, SnS, PbCuSbS3, Cu3AsS4 as well as CuIn1-xGaxSe (x > 0.5) are efficient electron reflector layer materials, so the potential improvement in efficiency obtained relative gain of 5%.