The induced modifications of the optical and surface characteristics in the annealed α-irradiated polycarbonate/polybutylene terephthalate (PC/PBT) blend have been studied in the temperature annealing range from 100 to 200 °C for 15 min. Several techniques have been used to study the changes in chemical composition, optical-electronic transitions, photoemission, contact angle, surface roughness, and hardness of annealed samples comparable to the pristine one. The FTIR spectra exhibit aggregate changes in the band intensities after annealing, indicating the scission and cross-linking of the polymer chains. The intensity of the peaks reduced with α-irradiation but began to increase with increasing annealing temperature. The trend of the function groups found in the annealed samples with the rise in annealing temperature supports the crosslinking mechanism. The UV/Vis spectra revealed that the absorption edges of annealed samples were shifted toward lower photon energy (red shift), reflecting the decrease of optical energy gap from 4 eV to 3.6 eV for direct transition and from 3.8 eV to 3.5 eV for indirect transition at the highest temperature. Further, the number of carbon atoms and the number of carbon clusters increases with the increase in the annealing temperature. The refractive index of the samples decreases from 1.5479 for the pristine sample to 1.4008 for the sample at the highest temperature. Moreover, the dielectric parameters and optical conductivity of the annealed samples were modified after thermal annealing. The PL emission yields are decreased with the increase in annealing temperatures that indicating an enhancement in the non-radiative recombination rate relative to the radiative recombination, which may be due to the increasing in the surface density states. The α-irradiated samples showed a notable increase in contact angle and a notable decrease in surface tension values with increasing the annealing temperatures. The side chain induction, which readily bundles and recombines the annealed parts by raising temperatures, also causes the surface roughness of annealed samples to decrease from 1.099 μm for the pristine sample to 0.696 μm for the annealed sample at the highest temperature. It is noteworthy that there is an increase in the hardness from 10.49 ΜPa for the pristine sample to 41.98 ΜPa for the annealed sample at the highest temperature. This is related to the results of changes in the polymer chains due to the active sites or branching points created by scission, which can lead to cross-linking.