In this work, Al2O3 coating effect on morphology, structure and optoelectronic properties of Si/SnO2/Al2O3 porous matrix composites (PMCs) were investigated. A three-staked thin layers deposited on a ⟨100⟩ oriented silicon substrate made these composites. First, porous silicon layers were achieved by electrochemical etching method. Then Al2O3 and SnO2 layers were successively deposited by physical and chemical vapor deposition, respectively. Morphological and micro-structural properties of the as prepared composites were evaluated by Scanning electron microscope, energy dispersive X-ray spectroscopy and X-ray diffraction. Results proved that Al2O3 concentration alters notably the porosity of the PMCs.Variable angle spectroscopic ellipsometry (SE) revealed a high correlation between the optical constants (n, k) and the PMC microstructure. Impedance spectroscopy revealed a semiconductor-metallic transition at high frequency in the temperature range between 340 to 410°C.