The effect of deposition of various polymer layers and annealing in the air at different temperatures on the surface photovoltage of CuInS2 photoabsorber films was studied. After polymer layer deposition onto the polycrystalline CuInS2 surface, roughness and photovoltage somewhat decreased. The photovoltage decrease is greater for polymers with smaller flexibility of macromolecules and can be caused by the formation of micropores in polymer films. After thermal annealing close to the polymer glass transition temperature micropores disappeared and photovoltage increased. Photovoltage increase was higher in the structures with the functional layer of polymers having larger flexibility of macromolecules.