Herein, the curing kinetics and the glass transition temperature (T_g) of MXene/phenolic epoxy composites with two curing agents, i.e., 4,4-diaminodiphenyl sulfone (DDS) and dicyandiamine (DICY), are systematically investigated using experimental characterization, mathematical modeling and molecular dynamics simulations. The effect of MXene content on an epoxy resin/amine curing agent system is also studied. These results reveal that the MXene/epoxy composites with both curing agent systems conform to the SB(m,n) two-parameter autocatalytic model. The addition of MXene accelerated the curing of the epoxy composite and increased the T_g by about 20 K. In addition, molecular dynamics were used to simulate the T_g of the cross-linked MXene/epoxy composites and to analyze microstructural features such as the free volume fraction (FFV). The simulation results show that the introduction of MXene improves the T_g and FFV of the simulated system. This is because the introduction of MXene restricts the movement of the epoxy/curing agent system. The conclusions are in good agreement with the experimental results.