Pure and Mn2+ doped poly(vinyl chloride) (PVC) polymer films were prepared using the solution cast technique. The prepared samples have been characterized by X-ray diffraction (XRD), UV-Vis Spectroscopy (UV-Vis), Fourier transform infrared (FTIR) Spectroscopy, Thermogravimetric analysis (TGA), Differential Scanning Calorimetry (DSC), Electron Paramagnetic Resonance (EPR) and Scanning Electron Microscopy (SEM) studies. TGA/DSC analysis reveals that the sample is thermally stable upto 350 0C. The morphology of the polymer films was studied by SEM. The optical absorbance of the polymer films was measured in the 200-900 nm wavelength range. The absorption edge, direct band gap and indirect band gap have been evaluated. The FTIR spectrum exhibits several bands characteristics of stretching and bending vibrations of C - Cl, C - H, C = C and O - H groups. The EPR Spectra at room temperature were used to calculate the number of spins and paramagnetic susceptibility as a function of dopant concentration. All the Mn2+ doped PVC samples exhibit a signal centred at geff = 1.9. The observed variation in the EPR signal intensity is due to the variation in the dopant concentration. The complexation of Mn2+ ion with the polymer was confirmed by XRD studies.