In next-generation EUV lithography, stochastic nanoparticle aggregation in photoresists(PR) causes resolution degradation and increased line edge roughness(LER). While previous studies focused on powder or solution phases, conventional analysis has been limited in characterizing structural evolution in thin-film states. In this study, we elucidated the correlation between thin-film nanostructures and lithographic performance via synchrotron X-ray analysis. Through GI-SAXS/WAXS, we confirmed that specific stabilizers maintain uniform nano-domains and analyzed the directional orientation of aggregation and its potential relationship with LER. Concurrently, thin-film XAFS was used to investigate the local coordination environment of metal centers, focusing on changes in coordination numbers and bond distances induced by ligands or stabilizers. These findings prove that nanostructural features within the actual thin-film are fundamental indicators determining the final lithographic performance.