Study of structural, optical and photocatalytic properties of multilayered (1–8 layers) zinc oxide films deposited on glass substrates by sol-gel method showed, that after thermal treatment at 500°C they consist of random oriented hexagonal crystalline grains with size of 34–40 nm, forming larger particles with sizes of 100–150 nm, which do not depend on number of layers. With an increase in the number of layers, the intensity of exciton photoluminescence decreases by a factor of 10, the absorption of light in the visible and near IR ranges increases, and the efficiency of photocatalytic decomposition of the test organic dye rhodamine B increases by 10–12%. The observed changes are related to the increase in the total area of grain boundaries and to the change in the integral amount of oxygen vacancies and interstitial atoms as the number of layers increases, which makes it possible to control the properties of zinc oxide films for applications in optoelectronics, photovoltaics and photocatalysis.