Several ways using surface modification are commonly used to enhance thermal stability of polymer matrices. In this study, Continuous-Wave carbon dioxide (CW CO2) laser irradiation and atmospheric pressure non-thermal He plasma treatment on microporous poly(vinyl chlo-ride)/Silica composite have been investigated and compared. On one hand the alternative was based on the efficiency of the thermal energy afforded by CW CO2 laser irradiation and induced photodegradation processes to release HCl and form polyene sequences under well-controlled condition. On the other hand atmospheric plasma treatment involved surface modification by formation of unstable radicals, inducing crosslinking and dehydrochlorination. In both cases a global thermal stabilization of the composite was noticed by partial dehydrochlorination of PVC, even for short exposure time. The main effects observed after laser irradiation were related to the formation of a very dense structure on surface with very low chlorine content and an important chlorine atoms in-depth gradient on the cross section up to 150 μm in thickness; whereas atmospheric He plasma treatment led to a homogeneous decrease of the chlorine in-depth content due to the plasma interpenetration in the porous microstructure. Structural and chemical modifications both on extreme surface and in the thickness have been investigated respectively by Environmental Scanning Electron Microscope (ESEM) coupled with an Energy Dispersive X-ray analysis (EDX) and X-ray Photoelectron Spectroscopy (XPS). Composites thermal stability and investigation on chlorine release have been evaluated by Thermo Gravimetric Analysis (TGA) coupled with Mass Spectrometry (MS).