Biomass pyrolysis and polypropylene (PP) pyrolysis in a stirred tank reactor exhibited different heat transfer phenomena whereby heat transfer in biomass pyrolysis was driven predominantly by heat radiation and PP pyrolysis by heat convection. Therefore, co-pyrolysis could exhibit be expected to display various heat transfer phenomena depending on the feed composition. The objective of the present work was to determine how heat transfer, which was affected by feed composition, affected the yield and composition of the non-polar fraction. Analysis of heat transfer phenomena was based on the existence of two regimes in the previous research in which in regime 1 (the range of PP composition in the feeds is 0−40%), mass ejection from biomass particles occurred without biomass particle swelling, while in regime 2 (the range of PP composition in the feeds is 40−100%), mass ejection was preceded by biomass particle swelling. The co-pyrolysis was carried out in a stirred tank reactor with heating rate of 5 °C/min until 500 °C and using N2 gas as carrier gas. Temperature measurement was applied to pyrolysis fluid at the lower part of the reactor and small biomass spheres of 6 mm diameter to simulate heat transfer to biomass particles. The results indicate that in regime 1 convective and radiative heat transfers sparingly occurred and synergistic effect on the yield of non-oxygenated phase increased with increasing convective heat transfer at increasing %PP in feed. On the other hand, in regime 2, convective heat transfer was predominant with decreasing synergistic effect at increasing %PP in feed. The optimum PP composition in feed to reach maximum synergistic effect was 50%. Non-oxygenated phase portion in the reactor leading to the wax formation acted as donor of methyl and hydrogen radicals in the removal of oxygen to improve synergistic effect. Non-oxygenated fraction of bio-oil contained mostly methyl comprising about 53% by mole fraction, while commercial diesel contained mostly methylene comprising about 59% by mole fraction