Nanocomposite (NC) films of polyvinyl alcohol (PVA), lignosulfonate (Lg), and nanosized palladium (Pd) were synthesized by ex-situ casting method. Samples from the synthesized PVA-Lg/Pd NC films were irradiated with 5–100 kGy γ doses. The effect of γ doses on the structural, thermal, and optical characteristics of the NC films were studied using different characterization techniques. The results indicated that the γ irradiation improves the decomposition temperature from 227 to 239 °C, signifying an increase in the thermal stability of the NC films. This was accompanied by a reduction of the melting temperature due to the increase of the amorphous phase. This can be attributed to the dominance of crosslinking. On the other hand, the refractive index increased from 2.21 to 2.32 while increasing the γ dose up to 100 kGy. This was associated with a reduction of the optical bandgap from 3.49 to 3.30 eV, which could be attributed to the increase in the amorphous phase as a result of crosslinking. This indicates an enhancement of the spreading of the NPs inside the blend matrix due to γ irradiation. This results in a more compacted construction of the PVA-Lg/Pd NC films. Furthermore, we used the Commission Internationale de E’Claire (CIE) method to estimate the change in color among the irradiated NC films and the pristine film. The PVA-Lg/Pd NC attained a significant color difference value greater than five, meaning permanent color changes.