A multi-scale micromechanical model is proposed to predict the damage degree of hybrid fiber-reinforced concrete under or after high temperatures. The thermal degradation of hybrid fiber-reinforced concrete is generally composed of the damage of the cement paste caused by thermal decomposition and thermal incompatibility, the deterioration of aggregates and fibers, and the interfacial damage between aggregates and the matrix. In this multi-scale model, four levels of hybrid fiber-reinforced concrete structures are considered when the thermal damage degree is derived; namely, the equivalent calcium silicate hydrate (C–S–H) product level, the cement paste level, the concrete level, and the hybrid fiber-reinforced concrete level. At the cement paste level, thermal decompositions of C–S–H product and calcium hydroxide are taken into account. In addition, a dimensionless parameter of the crack density is introduced to represent the thermal cracking of the matrix. At the concrete level, the interfacial damage of aggregates is simulated by a spring–interface model, in which the interfacial parameters are assumed to be functions of temperature. Moreover, at the cement paste level and the hybrid fiber-reinforced concrete level, a sub-stepping homogenization method is proposed to determine the effective properties. Comparisons between previously published experimental data and predictions and discussions illustrate the feasibility of the proposed multi-scale model in predicting thermal damage of concrete and hybrid fiber-reinforced concrete.