Herein, we report a comprehensive investigation on the thermal transitions of thin films of poly [2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione -3,6-diyl)-alt-(2,2'
5',2"
5",2'"-quaterthiophen-5,5'"-diyl)]PDPP4T, poly[2,6-(4,4-bis-(2-ethy-lhexyl)-4H-cyclopenta [2,1-b
3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)] PCPDTBT, 1:1 blend of PDPP4T and PCPDTBT, and their composites with gold nanoparticles (AuNPs). The thermal transitions of these materials were studied using variable temperature spectroscopic ellipsometry (VTSE), with differential scanning calorimetry (DSC) serving as the reference method. Based on obtained VTSE results, for the first time, we have determined the phase diagrams of PDPP4T/PCPDTBT and their AuNPs composites. The VTSE measurements revealed distinct thermal transitions in the thin films, including characteristic temperatures corresponding to the pure phases of PDPP4T and PCPDTBT within their blends. These transitions were markedly different in the AuNPs composites compared to the neat materials, highlighting the unique interactions between the polymer matrix and AuNPs. Additionally, we explored the optical properties, surface morphology, and crystallinity of the materials. We hypothesize that the observed variations in thermal transitions, as well as the improvement in optical properties and crystallinity, are likely influenced by localized surface plasmon resonance (LSPR) and passivation phenomena induced by the AuNPs in the composite films. These findings could have important implications for the design and optimization of materials for optoelectronic applications.