The 70% polyvinyl alcohol/30% polyvinyl pyrrolidone (PVA/PVP) polymer blends, with different weight ratios of tetrapropylammonium iodide (TPAI) or tetrahexylammonium iodide (THAI) salt, were prepared using dimethyl sulfoxide (DMSO) as a solvent. The X-ray diffraction technique was used to trace the crystalline nature of the formed blends. The SEM and EDS techniques were applied to figure out the morphology of the blends. The variation in the FTIR vibrational bands was used to investigate the chemical composition and the effect of different salt doping on the functional groups of the host blend. The influence of the salt type (TPAI or THAI) and its ratio on the linear and nonlinear optical parameters for the doped blends were investigated in detail. Absorbance and reflectance are highly enhanced in the UV region reaching a maximum for the blend with 24% TPAI or THAI; so, it can be employed as shielding materials for UVA and UVB types. The direct (5.1 eV) and indirect (4.8 eV) optical bandgaps were reduced continuously to (3.52, 3.63 eV) and (3.45, 3.51 eV) while increasing the content of TPAI or THAI, respectively. The blend doped with 24% wt TPAI exhibited the highest refractive index (around 3.5 in 400–800 nm). The DC conductivity is affected by the content and type of salt, its dispersion, and blend-salt interaction. The activation energies of different blends were obtained by applying the Arrhenius formula.