To reduce the thermal-oxidative aging of asphalt and the release amount of harmful volatiles during the construction of asphalt pavement, a new composite anti-aging agent was developed. Since the volatiles were mainly released from saturates and aromatics during the thermal-oxidative aging of asphalt, expanded graphite (EG) was selected as a stabilizing agent to load magnesium hydroxide (MH) and calcium carbonate (CaCO₃) nanoparticles for preparing the anti-aging agents of saturates and aromatics, respectively. Thermal stability and volatile constituents released from saturates and aromatics before and after the thermal-oxidative aging were characterized using the isothermal Thermogravimetry/Differential Scanning Calorimetry-Fourier Transform Infrared Spectrometer test (TG/DSC-FTIR test). Test results indicate that anti-aging agents of EG/MH and EG/CaCO₃ effectively inhibit the volatilization of light components in asphalt and improve the thermal stability of saturates and aromatics. Then, the proportions of EG, MH, and CaCO₃ added in the developed composite anti-aging agent of EG/MH/CaCO₃ are 2:1:3 by weight. EG/MH/CaCO₃ plays a synergetic effect on inhibiting the thermal-oxidative aging of asphalt, and reduces the release amount of harmful volatiles during the thermal-oxidative aging after EG/MH/CaCO₃ is added into asphalt at the proposed content of 10 wt. %. EG plays a synergistic role with MH and CaCO₃ nanoparticles to prevent the chain reactions, inhibiting the thermal-oxidative aging of asphalt.