• The pyrolysis of adenine containing phthalonitrile (ADCN) resin is studied. • ADCN resin cured by powder metallurgy like method remains oligomers. • The HCN gas is clearly observed during pyrolysis. • The releasing of nitrogen-containing products are observed above 800 °C. • 5.The transformation of N-doped structures with increasing temperature was observed. The pyrolysis behaviors of bio-based adenine containing phthalonitrile resin (ADCN) processed by powder metallurgy-like process are studied through the thermogravimetric analysis (TGA), thermogravimetry coupled with Fourier Transform Infrared Spectroscopy and Mass Spectrometry (TG-FTIR-MS), X-Ray photoelectron spectroscopy (XPS) and Raman spectra. The results indicate the pyrolysis process of ADCN resin can be dived into four stages. In the first stage (400–500 °C), The weight loss of the sample is small which may be caused by the volatilization of some oligomers. The second and third stages (500–820 °C) correspond to the major degradation process, where the release of small molecular compounds including HCN, NH 3 , CH 4 , CO 2 , CO, H 2 O, benzene and its derivatives. In addition, the release amount of HCN is more than other phthalonitrile (PN) systems. In the fourth stage (600–1000 °C), with the increase of temperature, the degree of disorder in carbon material increase, and the forms of nitrogen transform from pyrrolic nitrogen (N-5) and pyridinic nitrogen (N-6) to quaternary nitrogen (N-Q), which is benefit for the application of carbon materials in the electrical field.