Pine cone (PC) is a potential biomass energy source and is rich in nonstructural substances (NSS). To understand the impact of these NSS on the pyrolysis behavior and its products, in this study, phenol alcohol extraction was used for the separation of NSS from PC (the PC after separation of NSS was labeled as A-PC), and then thermogravimetric analysis −Fourier transform infrared and PY-gas chromatography/MS detection techniques were used to conduct a systematic comparison of the thermal degradation behaviors and kinetics parameters of PC and A-PC. Results showed that the N content of PC was higher than that of other biomass, and the activation energies of PC and A-PC generally decreased at first and then increased as the conversion rate increased. Furthermore, the activation energy of PC decreased with conversion rates in the range of 0.25–0.30, while A-PC lagged significantly behind PC. On the other hand, the maximum absorption peak of CH₄ for PC was higher than that of A-PC, and the maximum absorption peak of CO₂ was quite the opposite. After extracting NSS from the PC, its activation energy was significantly increased.