A variety of unmodified and modified fumed silica A-300 and silica/titania (ST20 and ST76 at 20 and 76 wt.% of titania, respectively) was prepared to analyze features of their interactions with polar and non-polar adsorbates. The materials were studied using nitrogen adsorption-desorption, ethanol evaporation kinetics, infrared (IR) spectroscopy, thermogravimetry (TG), photon correlation spectroscopy, differential scanning calorimetry (DSC), DSC and TG thermoporometry, and quantum chemistry. Changes in surface structure of modified nanooxides with increasing hydrophobization degree ((sic)(MS)) from 20% to 100% have a strong affect on the textural characteristics of the materials and adsorption-desorption of various adsorbates. Confined space effects enhanced due to the location of adsorbates in narrow voids between nanoparticles lead to freezing-melting point depression for bound polar and non-polar adsorbates. The behavior of particles of modified nanooxides in aqueous and water/ethanol media is strongly altered due to enhanced aggregations with increasing value of (sic)(MS). All of these change are non-monotonic functions of (sic)(MS) which affects (i) rearrangement of nanoparticles, (ii) interactions with polar and nonpolar adsorbates, (iii) location of adsorbates in voids of different sizes, (iv) the clustering of adsorbates and formation of nearly bulk structures. (C) 2017 Elsevier B.V. All rights reserved.