In this paper, a third-order exponential time differencing scheme, named ETDRK3, was investigated for large time stepping in the computation of hypersonic non-equilibrium flow. The second-order Harten-TVD scheme was used for the spatial discretization. The efficient implementation of the scheme with diagonalization of Jacobin matrix was established and carried out for the semi-cylindrical around flow. Current observations showed that the numerical results were in good agreement with those obtained by the classical explicit three-stage Runge-Kutta scheme (RK3) and implicit LU scheme. Efficiency assessments promised the effectiveness of the ETDRK3 scheme. The rationality of the application of this scheme was proved by its preferable accuracy and efficiency.