The performance of photovoltaics with superstrate configuration is limited by the rigidity and low refractivity of a classical glass cover. In this work, two polyimides (PIs) and two copolyimides combined in the main chain cycloaliphatic moieties, aromatic sequences, chalcogen atoms, and having/lacking fluorine atoms, are proposed as shielding covers for solar cells. The samples containing small cycloaliphatic moieties displayed high transmittance above 80% at 550 nm. The refractive index values under changeable wavelengths and temperatures were shown to influence the magnitude of the reflection losses. At the sample interface with the transparent electrode, optical losses were reduced (~0.26%) in comparison to the classical glass (~0.97%). The samples with the best optical features were further subjected to a surface treatment to render the self-cleaning ability. For this, a new approach was used residing in irradiation with the diffuse coplanar surface barrier discharge (DCSBD), followed by spraying with a commercial substance. Scanning electron microscopy and atomic force microscopy scans show that the surface characteristics were changed after surface treatment, as indicated by the variations in root mean square roughness, surface area ratio, and surface bearing index values. The proposed PI covers diminish the optical losses caused by total internal reflection and soiling, owing to their adapted refractivity and superhydrophobic surfaces (contact angles > 150°), and open up new perspectives for modern photovoltaic technologies.