In this work, results of measurements of surface tension of KOH and TMAH solutions containing alcohol additives were used to assess the behavior of the alcohols during silicon anisotropic etching. Surface tension of KOH and TMAH solutions containing additives of alcohols with one or more hydroxyl groups as well as etching rates and surface roughness of Si(100) and Si(110) surfaces etched in these solutions were analyzed. An improvement in roughness of both the planes was observed after addition of the alcohols to the KOH and TMAH solutions, however reduction of etching rates of Si(110) planes occurred only in KOH solutions. Based on surface tension measurements, it was stated that reduction of etching rates results from selective adsorption of the surface active compound on Si surfaces, which is possible due to adsorption layer formed on the solution surface of KOH etchant. The adsorption layer does not appear in TMAH + alcohols solutions, which accounts for a different behavior of TMAH-based etchants.