Clarifying the occurrence and morphological characteristics of petroleum hydrocarbons (PHs) in soil can facilitate a comprehensive understanding of their migration and transformation patterns in soil/sediment. Additionally, by establishing the dynamic transformation process of each occurrence state, the ecological impact and environmental risk associated with PHs in soil/sediment can be assessed more precisely. The adsorption experiments and closed static incubation experiments was carried out to explore the PHs degradation and fraction distribution in aged contaminated soil under two remediation scenarios of natural attenuation (NA) and bioaugmentation (BA) by exogenous bacteria through a new sequential extraction method based on Tenax-TA, Hydroxypropyl-β-cyclodextrin and Rhamnolipid (HPCD/RL), accelerated solvent extractor (ASE) unit and alkaline hydrolysis extraction. The adsorption experiment results illustrated that bioaugmentation could promote the desorption of PHs in the adsorption phase, and the soil-water partition coefficient Kd decreased from 0.153 L/g to 0.092 L/g. The incubation experiment results showed that compared with natural attenuation, bioaugmentation could improve the utilization of PHs in aged soil and promote the generation of non-extractable hydrocarbons. On the 90th day of the experiment, the concentrations of weakly adsorbed hydrocarbons in the natural attenuation and bioaugmentation experimental groups decreased by 46.44% and 87.07%, respectively, while the concentrations of strongly adsorbed hydrocarbons and non-extractable hydrocarbons increased by 77.93%, 182.14%, and 80.91%, and 501.19%, respectively, compared their initial values. We developed a novel dynamic model and inverted the kinetic parameters of the model by the parameter scanning function and the Markov Chain Monte Carlo (MCMC) method based on the Bayesian approach in COMSOL Multiphysics® finite element software combined with experimental data. There was a good linear relationship between experimental interpolation data and model prediction data. The R2 for the concentrations of weakly adsorbed hydrocarbons ranged from 0.9953 to 0.9974, for strongly adsorbed hydrocarbons from 0.9063 to 0.9756, and for non-extractable hydrocarbons from 0.9931 to 0.9982. These extremely high correlation coefficients demonstrate the high accuracy of the parameters calculated using the Bayesian inversion method.