The aging processes of microplastics (MPs) are prevalent in natural environments. Understanding the aging mechanisms of MPs is crucial for assessing their environmental behavior and potential risks. In this study, we selected polylactic acid (PLA) and polyethylene (PE) as representatives of biodegradable and conventional plastics, respectively, to examine changes in their physicochemical properties induced by water and UV light exposure. Laboratory aging resulted in significant fragmentation, characterized by cracks and pores on the surfaces, for both types of MPs, with PLA MPs exhibiting more severe changes, particularly under combined UV and water exposure. Notably, PLA MPs tended to become progressively smaller after aging, whereas PE MPs did not show significant size changes. Chemical analyses of aged MPs using micro-Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) revealed a substantial increase in the carbonyl index (CI) and oxygen content for PE, suggesting surface oxidation during photo-oxidation. Conversely, PLA MPs displayed a CI decrease, along with an oxygen content increase, indicating the breakdown of ester linkages in PLA and the formation of other oxidation products. Furthermore, we developed and optimized pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS) methods to identify potential chemical degradation products of PE and PLA, considering their differing thermal stabilities. We observed a distinct trend regarding the peaks in the chromatogram of aged MPs and identified the typical oxidation and crosslinking products for PLA. Additionally, after the aging process, both PE and PLA exhibited a significant increase in organic carbon content, with the eluate containing submicron/nano-sized particles. This study provides a scientific foundation for a deeper understanding of the environmental aging mechanisms of various MPs, particularly in regards to the effects of UV irradiation and water exposure.