The influence of PVA on the pyrolysis was studied from macro and micro angles. In this paper, briquette pyrolysis was operated with thermal analyzer. The experimental data showed that with the increase of PVA content, the R value, the reaction rate and the low calorific value increased. The FTIR spectrum, BET, industrial analysis and quantum chemical analysis were described that the addition of PVA was advantage to briquette pyrolysis. The number of micropores was increased and the heat and mass transferation was improved among the fuel layer with the addition of PVA.