Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)The quality of molecularly imprinted recognition sites depend on the mechanisms and the extent of the functional monomer-template interactions present in the prepolymerization mixture. Thus, an understanding of the physical parameters governing these interactions is key for producing a highly selective molecularly imprinted polymer (MIP). In this paper, novel molecular modeling studies were performed to optimize the conditions for the molecular imprinting of fenitrothion. Four possible functional monomers were evaluated. Five porogenic solvents were investigated employing the polarizable continuum method. The MIP based in methacrylic acid (MAA-MIP) synthesized in the presence of toluene shown to be the most thermodynamically stable complex. Contrarily, MIP based in p-vinylbenzoic acid (PVB-MIP) had the lowest binding energy. According to the adsorption parameters fitted by the Langmuir-Freundlich isotherm, MAA-MIP presented twice the number of binding sites compared to PVB-MIP (103.35 and 53.77 mu mol g(-1), respectively).254619628Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)CNPq [141618/2010-8]FAPESP [2007/02306-9]