The influences of four heating rates on the combustion and pyrolysis behavior in the N₂ and air atmosphere were investigated by the Fourier transform infrared spectrometry (FTIR) and thermogravimetric (TG) analysis. the distributed activation energy model (DEAM) and Flynn-Wall-Ozawa (FWO) were used to estimate Ea and A, ΔH, ΔG and ΔS. Experimental results showed that the similar thermal behavior emerged, but the temperatures in the air and N₂ atmospheres representing the end of the reaction were about 500 °C and 550 °C, respectively. The results of FTIR showed the peak positions were basically the same, but the concentrations of aromatics, aldehydes and ketones produced by pyrolysis in the N₂ atmosphere were higher. When the heating rate was 20 K/min, the comprehensive combustion parameters were 56.442 and 6.871 × 10⁻⁷%²/(min²• K³) in the air and N₂ atmospheres, respectively, indicating that the peanut shells had great potential to become bioenergy.