In the framework of the cluster approach ab initio calculations of the adsorption complexes of acetone molecule with an isolated terminal OH group of a silica gel (S1), with the fragment including hydrogen-bonded OH group (S2) and with two separated terminal OH groups simulating bifurcated acetone interaction (S3) were carried out. It is found that the difference between the stability of acetone complexes S1 and S2 is insignificant, and it is concluded that the bifurcated acetone interaction could result in a more stable adsorption form of acetone with the silica gel.