Modelling rarefied hypersonic reactive flows using the direct simulation Monte Carlo method. This paper presents the implementation, validation and application of TCE (total collision energy) model for simulating hypersonic reactive flows in a parallel direct simulation Monte Carlo code, named PDSC++, using an unstructured grid. A series of benchmarking test cases, which include reproduction of theoretical rate constants in a single cell, 2D hypersonic flow past a cylinder and 2D-axisymmetric hypersonic flow past a sphere, were performed to validate the implementation. Finally, detailed aerothermodynamics of the flown reentry Apollo 6 Command Module at 105 km is simulated to demonstrate the powerful capability of the PDSC++ in treating realistic hypersonic reactive flow at high altitude.