A mesoporous n-type silicon/poly (3'-acetic acid-2,2'-5',2 '' terthiophene)-(Poly (3TAA) nanocomposite was elaborated in order to realize new components for optoelectronics. Non-oxidized and oxidized porous silicon substrates is used and their physical and chemical properties have been studied by different techniques such as transmission electron microscopy (TEM), scanning electron microscopy (SEM) and Fourier transformed infrared spectroscopy (FTIR). Terthiophene based conjugated structure has been successfully incorporated inside the pores by capillarity at the melting temperature of the monomer. The filling of the monomer into the porous volume was probed by energy dispersive X-ray spectroscopy (EDX). Polarized infrared absorption spectroscopy results indicated that the monomer molecules show preferential orientation along the pore axis, due to hydrogen bonding, in particular that of the carboxylic groups with silanol-rich oxidized porous silicon surface. The 3TAA monomer molecules embedded in porous silicon matrix were electrochemically polymerized in situ and resonance Raman scattering spectroscopy proved the above-mentioned polymerization. (C) 2012 Elsevier B.V. All rights reserved.