Heterogeneous photocatalysis increasingly requires rapid polymer degradation tests relevant to aqueous conditions. In this study, a multi-technique approach was developed to monitor the early-stage photo-oxidation of polyethylene (PE) and polystyrene (PS) microplastics in an aqueous ZnO–TiO₂ suspension under combined ultraviolet A and ultraviolet B (UV-A/B) irradiation. The changes were analyzed by ATR-FTIR and Raman spectroscopy, DSC, and gravimetric measurements. For PE, the carbonyl index increased from 0.0189 to 0.1350 after 12 h, mass loss reached 16.98%, and crystallinity decreased from 32.05% to 25.36% after 8 h. The Raman spectra of PE showed band broadening and intensity redistribution, indicating increasing structural disorder. In contrast, PS showed weaker Raman changes, while FTIR revealed a non-monotonic carbonyl-index response, and DSC showed a 2.2 °C increase in Tg after 12 h. Gravimetric analysis also showed measurable mass loss in PS, reaching 18.62% after 12 h. The results demonstrate that the combined use of ATR-FTIR, Raman, DSC, and gravimetry enables reliable distinction between early oxidation, surface modification, and material erosion in photocatalytically treated microplastics.