The co-pyrolysis of biomass and fossil fuels has been the subject of studies on sustainable energy. Co-feeding oil shale with woody biomass can contribute to a transition into carbon neutrality. The present study analysed the thermal decomposition behaviour of oil shale and biomass blends (0:1, 3:7, 1:1, 7:3, 9:1, and 1:0) through thermogravimetric analysis (TGA) at 80–630 °C with a heating rate of 10 °C/min in CO2 and N2 atmospheres. A comparison of theoretical and experimental residual mass yields of oil shale–biomass mixtures indicated no significant interactions between the fuels. The blends contributed to a decrease of up to 34.4 wt% in solid residues compared to individual pyrolysis of oil shale, and the TGA curves were shifted from up to 10 °C to a lower temperature when the biomass ratio increased. The use of a CO2 atmosphere resulted in the production of solid residues, comparable to the one obtained with the N2 atmosphere. CO2 atmosphere can be used in oil shale–biomass co-pyrolysis, without affecting the decomposition process or increasing the yield of residues. A kinetic model method is proposed based on TGA data at 10, 20, and 30 °C/min. The apparent activation energies for a temperature range of 200–520 °C were in the order of 139, 155, 164, 197, 154, and 167 kJ/mol for oil shale–biomass 0:1, 3:7, 1:1, 7:3, 9:1, and 1:0 blends, respectively. From the isoconversional kinetic analysis, a two-stage pyrolysis was observed, which separated biomass and oil shale pyrolysis. A simulation of biomass and oil shale co-pyrolysis was conducted in Aspen Plus® using TGA-derived kinetic data. The model prediction resulted in a close match with the experimental thermogravimetric data with absolute errors from 1.75 to 3.78%, which highlights the relevance of TGA analysis in simulating co-pyrolysis processes.