Mixed antioxidants composed of antioxidant IPPD and novel rare earth lanthanum complex were used as an additive to prepare natural rubber (NR) samples. The variations of macro-properties, surface characterizations, and internal groups were investigated by mechanical testing, X-ray photoelectron spectroscopy, and thermogravimetric analysis coupled with Fourier transform infrared spectroscopy (TGA/FT-IR), respectively, to study the thermal-oxidative stability of NR. The thermal-oxidative degradation kinetic parameters were determined by analyzing the thermogravimetric curves at different heating rates with two model-free methods, Kissinger method and Flynn–Wall–Ozawa method. The results all showed that, compared with pure antioxidant IPPD, the same mass of mixed antioxidants could indeed improve the thermal-oxidative stability of NR. Furthermore, based on the TGA/FT-IR results and quantum mechanics simulations, the autocatalytic, free radical chain reaction mechanism for the thermal-oxidative aging of NR was clarified, and the different function mechanisms of antioxidants IPPD and p-ASALa were also discussed. Except for functioning as a labile-hydrogen donor which is similar to antioxidant IPPD in protecting NR against autoxidation, p-ASALa has strong coordination abilities and large coordination numbers, resulting in the high efficiency in enhancing the thermal-oxidative stability of NR.