The reasons why the open circuit voltage (Voc) of high-x CuIn1-xGaxSe2 (CIGS)/ZnO solar cells remain low are discussed. Here it is shown that the Voc ceiling can be interpreted simply on the basis of a model that the valence-band energy (Ev) of CIGS is almost immovable irrespective of x. When the conduction-band energy (Ec) of ZnO is lower than that of high-x CIGS (DEc<0), the built-in potential (Vbi) of a CIGS/ZnO junction is equivalent to the flat-band potential (Vbi) that arises from the separation between the Fermi energies of the two materials. If the Ev (and therefore the Fermi energy) of p-type CIGS is constant with increasing x, the Vbi and Voc that follows the Vbi remain unchanged since the Fermi energy of ZnO is constant. This unchangeable Voc reduces the conversion efficiency of high-x CIGS cells in cooperation with reduced photocurrents due to a larger bandgap. A positive offset, ΔEc>o gives rise to a photoelectrons barrier in the conduction-band that partially cancels Voc, thus the Voc of a low-x CIGS cell is governed by the Ec of CIGS. Based upon this concept, a material selection guideline is given for the windows and transparent electrodes appropriate for high-x CIGS absorbers-based solar cells.