This paper synergistically addressed the microstructure alteration and the mechanical behavior of rubber during thermo-oxidative aging process from both experimental and numerical modeling aspects. Through the FTIR spectra analysis, equilibrium swelling experiment, low-field NMR measurement and mechanical tests of styrene-butadiene rubber (SBR) samples, a macromolecular network alteration mechanism was introduced. The mechanism is related to the variation of the crosslinking network and dangling chain ends of SBR during aging. A finite deformation based hyper-viscoelastic constitutive model was then established to capture the mechanical behavior of SBR during aging. Based on the interpretation of the microscopic mechanism, the above-mentioned network alterations during aging were considered in the model. After the implementation by means of the finite element simulation software ABAQUS, the accuracy of the established model was checked via the comparison of the numerical results with the corresponding data obtained from mechanical tests. The work is helpful for estimating rubber mechanical performance during aging process.