Microplastics (MPs) coexist with plasticizers in the aqueous environment to form composite pollution, but the adsorption and desorption behaviors of MPs and plasticizers under natural conditions are unknown. Polyvinyl chloride (PVC) and rubber were used as the target MPs to characterize the changes in their morphological features after aging for one anniversary in atmospheric exposure and lake sedimentary burial environments and to investigate the adsorption and desorption behavior of the MPs to the coexisting phthalate esters (PAEs) plasticizer before and after aging. The results showed that the surface of MPs was rougher after exposure to the atmospheric environment and burial in a depositional environment, showing the characteristics of porous polymers. The carbonyl index (CI) of PVC and rubber increased by 62.2% and 321.2%, respectively, in the atmospheric environment and increased by 51.1% and 223.1%, respectively, in the depositional environment. The atmospheric exposure was capable of accelerating the aging process of MPs. PAEs were adsorbed on the surface of MPs through hydrophobic interaction, and the amount of adsorption was significantly and positively correlated with their hydrophobic properties. The adsorption capacity and adsorption rate of PVC on PAEs were inhibited after aging. Aging promoted the adsorption of rubber on strongly hydrophobic PAEs plasticizers and inhibited the adsorption of weakly hydrophobic PAEs. The environmental aging process reduced the desorption of strongly hydrophobic PAEs from rubber, enhanced the reversibility of rubber adsorption of weakly hydrophobic PAEs, and increased the desorption rate of PAEs from PVC.