To better understand the biomass waste pyrolysis, a series of thermogravimetric experiments of basswood waste was performed at various heating rates in an inert atmosphere. Two model-free methods including Flynn-Wall-Ozawa (FWO) and Kissinger-Akahria-Sunose (KAS) and one model-fitting method named Coats-Redfern (CR) coupling Shuffled Complex Evolution (SCE) method were used in this work. The pyrolysis behaviors of hemicellulose and cellulose are responsible for the shoulder peak and the main peak. The evolution of activation energy supports the pyrolysis process divided into two regions. The 3D diffusion-Jander model (D3) can be used to describe the pyrolysis process of basswood waste. The optimized kinetic parameters estimated by the SCE algorithm coupled with a three-component parallel reaction scheme. The predicted values match the experimental data well, which shows that the optimized kinetic parameters are potentially promising in evaluating the biomass waste pyrolysis.