Here we demonstrated the prospects to create effective and profitable organic multitextures for the frontal surface of the hybrid structure of solar cells by using a sol-gel method on macro- or mesoporous silicon. A problem of obtaining the desired size and depth of a macrotexture was investigated by using the additions of organic origin (organic acids, ketones, alcohols) in etchants. In the course of the present study, we managed to experimentally determine optimal conditions for receiving macro porous surface macro texture of silicon substrates. Formed by chemical methods of treatment, the surface of a silicon substrate of solar cell makes it possible to attain several significant advantages, the main of which is the existence of relief, enabling conducting the subsequent technological stages (fabrication of an organic multilayer stack using the sol-gel technology), which, if combined, can create on the surface of a silicon substrate a high quality optical system to capture luminous flux. Development of the technological process for the synthesis of sol-gel method was carried out using a low-molecular polymer and applying an AR coating, which represents spatial-crosslinked condensation structures of organosilicon gel – xerogel of polyorganosiloxane. This will make it possible to create a multifunctional organic multitexture for the frontal surface of a solar cell using hybrid technologies for obtaining PS, with a reduced cost of production, relatively large efficiency and simple technological process of the synthesis, which can be applied over large areas. Parameters of the multifunctional organic multitextures, which were created at the macro surfaces of substrates for SC, were explored using the method of mass spectrometry.