We derive the second-order hydrodynamic equation and the microscopic formulae of the relaxation times as well as the transport coefficients systematically from the relativistic Boltzmann equation. Our derivation is based on a novel development of the renormalization-group method, a powerful reduction theory of dynamical systems, which has been applied successfully to derive the non-relativistic second-order hydrodynamic equation. Our theory nicely gives a compact expression of the deviation of the distribution function in terms of the linearized collision operator, which is different from those used as an ansatz in the conventional fourteenmoment method. It is confirmed that the resultant microscopic expressions of the transport coefficients coincide with those derived in the Chapman-Enskog expansion method. Furthermore, we show that the microscopic expressions of the relaxation times have natural and physically plausible forms. We prove that the propagating velocities of the fluctuations of the hydrodynamical variables do not exceed the light velocity, and hence our second-order equation ensures the desired causality. It is also confirmed that the equilibrium state is stable for any perturbation described by our equation.