Poly (vinyl chloride) (PVC), ethylene vinyl acetate (EVA), and PVC/EVA (50/50 wt%) samples were synthesized using casting technique. The as-prepared samples were irradiated with various fluencies of nitrogen ion beam, using a broad beam cold cathode ion source. The structural, optical and thermal properties of pristine and irradiated samples were investigated using FTIR, XRD, UV-VIS, and TGA analytical techniques. FTIR and XRD investigation showed several changes in the crystal structure, intensity and position of the characteristic peaks for the investigated samples. The optical band gap energies for both PVC and EVA samples is being to decrease with increasing ion beam fluence, whereas 50/50 wt% PVC/EA blend sample exhibits an increment behavior as a result of increasing ion beam fluence. The thermal stability of ion beam bombarded samples decreased for PVC and EVA samples than that for pristine samples, whereas a noticeable increase in the stability of the 50/50 wt% PVC/EVA blend samples. It is clear that thermal decomposition is affected by nitrogen ion beam fluencies owing to the extent of crosslinking and degradation processes. The results showed that nitrogen ion beam bombardment significantly affect the physico-chemical properties of PVC, EVA, and PVC/EVA samples.