Methyl-terminated poly(dimethylsiloxanes) (PDMSs) are typically considered to be inert and not suitable for surface functionalization reactions because of the absence of readily hydrolyzable groups. Nevertheless, these siloxanes do react with silica and other oxides, producing chemically grafted organic surfaces. Known since the 1970s and then forgotten and recently rediscovered, this reaction provides a versatile yet simple method for the covalent functionalization of inorganic surfaces. In this work, we have explored the reactions of linear methyl-terminated and cyclic PDMS and bis-fluoroalkyl disiloxanes for the surface functionalization of mesoporous silica (Dpore approximate to 30-35 nm). The optimal reaction conditions included 24 h of contact of neat siloxane liquids and silica at 120-250 degrees C (depending on the siloxane). A study of the reactions of silicas with different extents of hydration demonstrated the critical role of water in facilitating the grafting of the siloxanes. The proposed reaction mechanism involved the hydrolysis of the adsorbed siloxanes by the Lewis acidic centers (presumably formed by water adsorbed onto surface defects) followed by the coupling of silanols to the surface to produce grafted siloxanes. For rigorously dehydrated silicas (calcination similar to 1000 degrees C), an alternative pathway that did not require water and involved the reaction of the siloxanes with the strained siloxane rings was also plausible. According to FTIR and chemical analysis, the reactions of bis-fluoroalkyl disiloxanes and cyclic PDMS (D-3-D-5) produced covalently-attached monolayer surfaces, and the reactions of high-MM methyl-terminated PDMS produced polymeric grafted silicas with a PDMS mass content of up to 50%. As evidenced by the high contact angles of similar to 130 degrees/100 degrees (adv/rec) and the negligible amount of water adsorption over the entire range of relative pressures, including saturation (p/p(0) -> 1), the siloxane-grafted porous silicas show uniform, high-quality hydrophobic surfaces. An overall comparison of siloxanes with classical silane coupling agents (i.e., silanes with readily hydrolyzable functionalities such as chloro, amino, etc.) demonstrated that the reactions of siloxanes produced surfaces of similar quality and, although requiring higher temperatures, used noncorrosive, less hazardous reagents, thereby providing an environmentally benign alternative to the chemical functionalization of metal oxide surfaces.