Electrostatic guidelines have been employed to explore weak complexes of naphthalene and its methoxy- and cyano-derivatives. The initial geometries of these complexes are obtained from the electrostatic potential for intermolecular complexation (EPIC) model, with a follow-up by ab initio calculations at the Hartree-Fock, density functional and second-order-Moller-Plesset (MP2) levels of theory. The EPIC model is seen to provide starting structures and energetic trends in good agreement with the ab initio ones. Further, the results of ab initio calculations are in conformity with the semi-qualitative conclusions regarding the geometries reached from spectroscopic experiments.