Films of polyvinyl alcohol (PVA) – polyvinyl pyrrolidone (PVP) blend doped with lead nitrate (Pb(NO3)2) were prepared by solution casting method, with doping level (DL) of Pb(NO3)2 in PVA – PVP polymeric blend varying from 2.7 up to 50.5 wt%. The prepared films were characterized using UV-Visible spectroscopy, fluorescence (or photo- luminescence) spectroscopy, FTIR and Raman spectroscopy. Parameters like optical band gaps due to indirect allowed transition (IAT) and direct allowed transition (DAT), as well as the activation energy (Ea) for optical transitions are extracted from the UV- Visible (or optical) spectra of these films. Objective of the FTIR, Raman and Fluorescence spectroscopic study is to understand the molecular chemical changes in PVA and PVP caused by the dopant (Pb(NO3)2). There is an enhancement of fluorescence intensity at DLs of 2.7 wt%, and at DL 7.6 wt%, the fluorescence intensity decreases (quenching). PVP acts as a capping agent for the dopant species, and is considered to be responsible for changes in fluorescence intensity. Signature of nitrate ion (NO3-) vibration is observed at wavenumber 1037 cm-1 in Raman spectra, and in the FTIR spectra, the NO3- vibration is seen at the wavenumber equal to 1380 cm-1.