To maximize the potential energy utilization of agricultural and forestry wastes and sludge, experimental studies were conducted on the co-gasification characteristics of two types of sludge (municipal sludge, MS; paper-mill sludge, PS) and a typical biomass straw (ST) under CO2 atmosphere. In this paper, the main two stages of the gasification process, the pyrolysis in the low-temperature region and the CO2-gasification in the high-temperature region, were separately studied and analyzed. The experimental results showed that biomass could effectively promote the pyrolysis of the sludge in the low-temperature region and improve the gasification in the high-temperature region. Due to the complex interactions between components, the characteristic parameters presented obvious nonlinear rules during the co-pyrolysis and co-gasification processes. For the MS-ST mixtures, when increasing the ST content, (i) in the pyrolysis process, the initial reaction temperature gradually decreased, but the final reaction temperature, the peak reaction rate and the corresponding temperature, and the pyrolysis index gradually increased; (ii) in the gasification process, the initial reaction temperature, the reaction final temperature, and the temperature corresponding to the peak gradually increased. Combined with the reaction kinetics analysis of the co-pyrolysis and the co-gasification processes, 25% may be a reasonable mixing ratio for ST for the MS-ST mixtures, which had a relatively lower reaction temperature, relatively high pyrolysis index and low activation energy (26.58 kJ·mol−1 and 178.29 kJ·mol−1 for the co-pyrolysis and co-gasification processes, respectively). For the PS-ST mixtures, when increasing the ST content, (i) in the pyrolysis process, the initial reaction temperature, the peak reaction rate, the temperature corresponding to the peak and the pyrolysis index gradually decreased, but the final reaction temperature gradually increased; (ii) in the gasification process, the initial and final reaction temperatures and the temperature corresponding to the peak gradually decreased, but the peak reaction rate gradually increased. Combined with the reaction kinetics analysis of the pyrolysis and the gasification processes, 25% may be a reasonable mixing ratio for ST for the PS-ST mixtures, which had a relatively lower reaction temperature, relatively high pyrolysis index and low activation energy (64.29 kJ·mol−1 and 301.16 kJ·mol−1 for the co-pyrolysis and co-gasification processes, respectively). These findings can provide useful information for the co-gasification of sludge and straw under CO2 atmosphere.