Sorption of the polar insecticide imidacloprid on organic-saturated octadecylammo-nium (CIS) and dioctadecyldimethylammonium (DOD) and inorganic- (Fe-) saturated Wyoming (W) and Arizona (A) montmorillonites has been investigated. Sorption isotherms were fitted to the Freundlich equation. Imidacloprid-montmorillonite complexes were studied by X-ray diffraction and FT-IR techniques. Imidacloprid sorption coefficients, Kf, decreased in the order WC18> AC18> WFe> WDOD⩾ ADOD. The low layer charge and saturation by primary alkylammonium cation facilitates sorption of imidacloprid in the interlayer of the smectite, corroborated by the increase in basal spacing observed in X-ray diffraction patterns and by the presence of absorption band shifts in FT-IR spectra. Imidacloprid sorbs in the interlayer space of smectite mainly by hydrophobic interactions with the alkyl chains in organic smectites and with the uncharged siloxane surface in Fe(III)-smectite. Further polar bonds between the NO2 group of imidacloprid and the NH of the primary alkyl cations and protonation of imidacloprid in Fe-smectites enhanced sorption in these cases.