Polyvinyl alcohol (PVA) − polyvinyl pyrrolidone (PVP) blend solutions were doped with different amounts of lead nitrate (Pb(NO3)2), in the doping range varying from 2.7 wt% up to 50.5 wt%. In this paper, the study of these films using Energy Dispersive X‐ray Fluorescence (EDXRF) technique in 2 π geometrical configuration is explained. In order to study K shell (Kαβ) X‐rays from the prepared films, cobalt‐57 radio‐isotope and thallium doped sodium iodide [NaI(Tl)] scintillation gamma/ x‐ray detector system with 1k MCA are used. The experiment was complemented by Scanning Electron Microscopy (SEM) coupled with Energy Dispersive X‐ray Spectroscopy (EDS). The SEM images revealed that the filler (Pb(NO3)2) causes significant micro‐structural changes in doped PVA/PVP blend films, revealing phase separation of the material into a polymer rich region and a dopant rich region at doping levels beyond 12.1 wt%. In addition to SEM, the EDXRF study is complemented by X‐Ray Diffraction (XRD) and Differential Scanning Calorimetry (DSC) scans on the Pb (NO3)2 doped PVA/PVP blend films.