We report the influence of the silanol group (Si-OH) of silica gel and mesoporous silica on the adsorption characteristics for various constituents in cigarette smoke. Comparing activated carbon, siliceous porous materials that have silanol groups selectively adsorbed the hydrophilic volatile constituents with saturated vapor pressure from 103 to 105 Pa at 298 K. Preparing the modified silica gel, the trimethylsilyl group (hydrophobic) replaced the silanol group (hydrophilic) to decrease the amount of hydrophobic groups. Adsorption efficiencies of hydrophilic volatile constituents on the modified silica gel were clearly lower than on unmodified silica gel. This result suggests the silanol groups play an important role in adsorption of the constituents, i.e. the groups adsorb the constituents by chemical interaction such as hydrogen bonding, electric dipole-dipole interaction. The adsorption performances of various silica gels and mesoporous silicas with the different number of silanol groups per gram were examined for volatile constituents. As a result, the larger the number of silanol groups, n, goes, the smaller the penetration efficiency, 1-E, in logarithmically, Ln (1 -E) =-K n. The K is the adsorption factor and shows a different value for each hydrophilic constituent. The correlation between K and the octanol-water partition coefficient, log P_ow , is expressed by K = -1.4 x 10^-22 Log P_ow + 3.5 x 10^-22 (r = -0.85). Consequently, it is found that (i) silanol groups selectively adsorb the hydrophilic volatile constituents by chemical interaction, and (ii) adsorption efficiency of each volatile constituent can be predicted by two parameters of the number of silanol groups of siliceous porous materials and log P_ow of each constituent.