Spontaneous combustion of coal has long been a thermal dynamic hazard during coal mining, storage, and transport, posing a great threat to coal mine safety. Especially coal spontaneous combustion in longwall goaf poses a great threat to underground working crew. To investigate such a mine safety issue with more insights and “what if” scenarios, this study employs CFD technique to develop a proactive inertisation plan in a longwall goaf. Based on real on-site conditions of the longwall goaf, a three-dimensional transient non-equilibrium thermal CFD model was developed to study heating evolution and proactive inertisation plans of the longwall goaf. The theoretical model incorporated a set of governing equations including low temperature kinetics of coal oxidation, energy and mass conservation, momentum balance, and continuity equation. After the base model (1000 m) was validated and calibrated with field gas monitoring data, another model (500 m model) was studied to obtain an optimum inertisation plan. Both steady state and transient simulations were conducted to study the flow dynamics of air velocity, oxygen ingress, dispersion of gaseous products and heating evolution in the longwall goaf. Based on the flow dynamics field, proactive inertisation plans using nitrogen to suppress the onset and development of goaf heatings were then developed and studied.