The purpose of this study was to investigate the effect on polystyrene (PS) during co-pyrolysis with biomass through thermal decomposition. The model-free iso-conversional methods (Kissinger, Friedman, Flynn-WallOzawa, Kissinger-Akahira-Sunose, Starink and Vyazovkin) were adopted to calculate activation energy of the pyrolysis and co-pyrolysis process of two biomass samples (walnut shell: WS and peach stones: PST) with PS. It is found that biomass blending to PS decreased activation energy values and resulted in multi-step reaction mechanisms. Furthermore, changes in the evolution profiles of methyl, water, methoxy, carbon dioxide, benzene and styrene was monitored through evolved gas analysis via TGA/FT-IR and TGA/MS. Detection of temperature dependent release of volatiles indicated the differences occur as a result of compositional differences of biomass.