The filling level (W) dependence of the local structure of MnCl2 through the PVDF matrix was explored. The presence of alpha- and beta-PVDF crystalline phases were detected by X-ray diffraction, and it was confirmed by the infrared (IR) absorption spectra. A significant head-to-head content was implied by IR spectroscopy. Two filling, level-dependent optical energy gaps were found through the UV-VIS spectral investigation. An intrachain one-dimensional interpolaron hopping mechanism was assumed to proceed in the temperature range of 350-375 K. The calculated values of the charge carrier hopping distance were in the range of 6.5-9.7 nm. The temperature dependence of the direct current (dc) magnetic susceptibility exhibited a Curie-Weiss behavior. Positive values of the paramagnetic Curie temperature (theta(p)) for W up to 14.5% indicated the presence of a ferromagnetic interaction, while negative theta(p) obtained for higher W values suggested an antiferromagnetic interaction at lower temperature. The electron spin resonance (ESR) analysis revealed the existance of both isolated and aggregated Mn2+ ions within the PVDF matrix.