The optical properties, namely refractive index (RI) studies, are reported on a series of pure and doped poly(vinyl alcohol) (PVA) in solution form. The PVA solutions were synthesized with 1, 2, 3, 4, and 5 wt% of PVA in distilled water followed by doping with Rhodamine B in concentrations ranging from 0.05 wt% to 2 wt%. The absorption spectra show an observable shift in the band edge position towards higher wavelength with increase in PVA wt%. When the dopant molecules are added, the curves are drastically modified with the occurrence of new peaks arising at higher doping concentrations along with change in the bandgap. These effects are prominent for all the concentration of PVA solution. The RI does not change much for low doping wt%. but when dopant is added in higher concentrations, it increases slightly reaching a maximum of ∼1.35 at 2 wt%. It is observed that host polymer properties dominate at low doping while a combination of host polymer and dopant dye properties dominate at higher doping concentrations.