Thin-layer molecularly imprinted polymer (MIP) composite membranes for selective binding of triazine herbicide desmetryn from aqueous solutions were developed using photoinitiated copolymerization of 2-acrylamido-2-methyl-1-propane sulphonic acid and N,N'-methylene-bis-acrylamide in the presence of template, followed by a deposition of MIP layer on the surface of either hydrophobic or hydrophilically precoated polyvinylidene fluoride (PVDF) microfiltration membranes. MIP membranes with different degrees of surface modification were prepared. It was shown MIP membranes provide a high selective binding of desmetryn from aqueous mixtures of structurally similar herbicides. It was concluded that MIP membrane binding specificity is a result of both multi-sites binding to the template via ionic and hydrophobic interactions and the correct position of functional groups involved in binding in imprints.