Volatile Organic Compounds are a cause of concern for human health. It is particularly the case for BTEX compounds (Benzene, Toluene, Ethylbenzene and Xylenes). Gravimetric sensors are good candidates for their detection but they have to be functionalized by a sensitive film to become active. In this work, organosilicate thin films (SiOCH) deposited by plasma enhanced chemical vapor deposition are investigated. This work aims at understanding the role of their chemical composition on gas adsorption and to propose an optimized material for BTEX detection. Through the synthesis and characterization of various SiOCH thin films, the role of hydrophobicity, carbon content and specific chemical bonding is highlighted. This led to an optimized film presenting both high affinity (partition coefficient toward toluene higher than 15000) and rapid temporal response.