Ephedrine is an illicit drug, classified as precursor for methamphetamine, which is also used as stimulant, appetite suppressant, decongestant or asthma. In this study, novel molecularly imprinted polymer (MIP) films were prepared by sol-gel derived techniques, using N-(2-aminoethyl)-3-aminopropyltrimethoxysilane as functional monomer, to recognize ephedrine from aqueous solutions. The films were obtained by air-spraying the precursor solutions, with various concentrations of monomer and template, on glass supports. Infrared, thermogravimetry, ellipsometry, optic and atomic force microscopy analyzes of films provided information regarding the effect of molecular imprinting upon the physical properties of films. Further on, batch rebinding evaluation indicated that thinner films present high affinity for ephedrine, resulting in 6.2 imprinting factor after 15 minutes of contact, which attests the ability of the novel MIP films to recognize and rebind ephedrine.