We have studied the heat treatment influence (room temperature to 400°C) on thin aminopropyltrimethoxysilane (APTMS)-based films incorporated with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), copper phthalocyanine (CuPc), and three-dimensional structure cage polyhedral oligomeric silsesquioxanes (POSS) by X-ray photoelectron spectroscopy and capacitance voltage technique. We discuss the interplay between the temperature degradation of the organic components (aminopropyl groups, sp 3 -based carbon bonds of APTMS, cyclopentyl rings, and vinyl functional group of POSS) and the thermal stability of the fullerene molecules (PCBM), benzene rings (CuPc), and the POSS inorganic cages. We observe the formation of Si-O-Si bridges between the POSS inorganic cages and the SiO 2 -enriched matrix which contains also fullerene molecules and benzene rings.