The present study employs X-ray photoelectron spectroscopy (XPS) to analyze plastic samples subjected to degradation processes with the aim to gain insight on the relevant chemical processes and disclose fragmentation mechanisms. Two model plastics, namely polystyrene (PS) and polyethylene (PE), are selected and analyzed before and after artificial UV radiation-triggered weathering, under simulated environmental hydrodynamic conditions, in fresh and marine water for different time intervals. The object of the study is to identify and quantify chemical groups possibly evidencing the occurrence of hydrolysis and oxidation reactions, which are the basis of degradation processes in the environment, determining macroplastic fragmentation. Artificially weathered plastic samples are analyzed also by Raman and FT-IR spectroscopy. Changes in surface chemistry with weathering are revealed by XPS, involving the increase in chemical moieties (hydroxyl, carbonyl, and carboxyl functionalities) which can be correlated with the degradation processes responsible for macroplastic fragmentation. On the other hand, the absence of significant modifications upon plastics weathering evidenced by Raman and FT-IR spectroscopy confirms the importance of investigating plastics surface, which represents the very first part of the materials exposed to degradation agents, thus revealing the power of XPS studies for this purpose. The XPS data on experimentally weathered particles are compared with ones obtained on microplastics collected from real marine environment for investigating the occurring degradation processes.