The aim of this study has been to examine in depth three siloxane resins (R1–R3) and two silanes (S1–S2) as hydrophobic self-cleaning layers for silicon and dye-sensitized solar cells. Herein, we focused on creating an active self-cleaning surface system using a combination of material and technical aspects. Siloxane resins were obtained via the hydrolytic polycondensation of methyltrimethoxysilane (R1) or the hydrolytic co-polycondensation of methyltrimethoxysilane, isobutyltrimethoxysilane and 3-methacroiloxypropyltrimethoxysilane (R2) or methyltrimethoxysilane n-octyltriethoxysilane and 3-methacroiloxypropyltrimethoxysilane (R3) under alkaline conditions using tetrahydrofuran. All layers under study did not significantly affect the original optical properties of the glass support, confirming that all these compounds can be used as protective layers on glass surfaces. The hydrophobic nature of formed layers was confirmed by static water contact angle measurements for hexane- and/or dibutyl ether-based starting solutions at various concentrations. The structural defects in created layers were studied via atomic force microscopy and thermal imaging, revealing RMS roughness (R_q) values in the range of 0.76–5.25 nm, which varied for different materials. The current–voltage curves of different hydrophobic coatings showed conductive behaviour, demonstrating that principally non-conductive coatings mixed with silver conductive paste showed a certain level of conductivity. This finding suggests that the hydrophobic coating resembles a porous structure, enabling the formation of electrically conductive pathways. Finally, the influence of the presence of a coating layer on silicon and dye-sensitized solar cells was studied, and no negative effect on their photovoltaic parameters was observed after the durability test.