In this study, the pyrolysis characteristics of sucrose biomass were investigated with a thermogravimetric analysis coupled with gas chromatography (TGA-GC) system at different temperatures and various heating rates. The gas products from sucrose pyrolysis were measured, and the results showed that the gas product consisted of a major amount of CO, CO2, H-2, and CH,. The temperature and addition of CaO could greatly affect the gaseous product yields. The distinct phases in the pyrolysis process of sucrose biomass were discussed. An improved iterative Coats-Redfern method was used to evaluate non-isothermal kinetic parameters for sucrose pyrolysis with/without the addition of CaO in different phases, and the activation energies and pre-exponential factors were calculated by means of linear regressions. The calculated results showed that the model with an Avrami-Erofeev mechanism could accurately be used to predict the main phase as well as the other phases for the pyrolysis processes.