Co-pyrolysis technology is considered to be one of the most promising methods for the sustainable utilization of biomass wastes, as it can realize waste reduction and convert wastes into high-value-added products with little impact on the environment. The evaluation of thermal characteristics and product properties is necessary for understanding this technique. In this paper, thermal characteristics and kinetic and thermodynamic analysis during the co-pyrolysis of mushroom residue (MR) with pine sawdust (PS) or wheat straw (WS) were investigated in a TGA. The carbon structure and surface textures of co-pyrolytic char were explored using Raman spectroscopy and a scanning electron microscope. As the PS or WS mass ratio increased, the devolatilization index increased obviously, indicating that volatile release was promoted and concentrated. Weak interactions were observed between 250 and 400 °C during the co-pyrolysis process, which primarily affected the mass transfer, resulting in a change in the thermal decomposition temperatures and rates. The interactions had no prominent influence on the volatiles’ yields. The non-additive performance of average activation energies for the blends was observed due to the interactions, and the lowest average activation energy was obtained when the PS or WS mass ratio was 50%. The lower average pre-exponential factor of the blends indicated the reduced complicacy of the pyrolysis reaction. The relatively small deviation between the activation energy and enthalpy change (4.94–5.18 kJ·mol−1) signified the energy sensitivity of product formation. PS promoted the formation of small aromatic rings (<6 fused rings) in co-pyrolytic chars, whereas WS favored the production of larger rings (≥6 fused rings). The surface textures of the co-pyrolytic chars became porous, and the greater fractal dimensions of the surface morphology for the co-pyrolytic chars indicated that the char surface became irregular and rough.
