AbstractSilica gel (320 m2g–1, 10 nm) was chemically modified with 3‐chloropropyltrimethoxysilane or 3‐aminopropyltrimethoxysilane, followed by reaction with aniline, 3‐phenylchloropropylamine, or benzylamine. The resulting silicas were characterized by elemental analysis and spectroscopic techniques, namely diffuse reflectance spectroscopy (DRS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and 29Si variable amplitude cross‐polarization magic‐angle spin nuclear magnetic resonance (VACP‐MAS‐NMR). The resulting solids were shown to be stable in aqueous and non‐aqueous media and were tested as sorbents for pre‐concentration of derivatized phenolic compounds (acetyl derivatives of: phenol, o‐cresol, m‐cresol, p‐cresol, 2‐ethylphenol, 3‐ethylphenol, and 4‐ethylphenol) and some organochloride pesticides (endrin, pentachlorobenzene, heptachloro epoxide, hexachlorobenzene, and lindane) in aqueous media. Extractionexperiments were undertaken using a precleaned cartridge (10 cm×10 mm ID) packed with modified silica gel and with commercial C‐18 in order to evaluate the influence of the nature of the functional group onretention of the compounds under study. Results showed that silica modified with aniline gave the highest retention for the studied acetylated phenolic compounds. Silica modified with 3‐phenylchloropropyl groups exhibited the highest retention for hexachlorobenzene and aldrin, while that modified with benzylamine showed the highest retentionfor eldrin, pentachlorobenzene, and heptachloro epoxide. Lindane was not retained by any of the tested materials.