A new strategy for synthesis of molecularly imprinted organically modified silica (MIORMOSIL) has been described. The MIORMOSIL was prepared by reacting vinyl acetate and 3-(trimethoxysilyl) propyl methacrylate, followed by condensation and hydrolysis with tetraethyl orthosilicate in the presence of caffeine. The ORMOSIL was characterized by SEM, FTIR, Si-29 MAS NMR, C-13 MAS NMR, TGA, nitrogen adsorption/desorption and tested to extract analyte from coffee samples. The percentage recovery of caffeine 885% (n=9), limits of detection and quantification, 5.14 x 10(-4) and 1.71 x 10(-3)mmolL(-1) respectively, were achieved. Cross reactivity studies for theophylline and theobromine showed high recovery (77% and 82% respectively).Abbreviations: HMIP: Molecularly Imprinted ORMOSIL; HNIP: non imprinted ORMOSIL; TMSPM: 3-(Trimethoxysilyl)propylmethacrylate