Herein, we report the preparation and characterization of a novel polymeric blend between linear polyethylene imine (PEI) and polyacrylonitrile (PAN), with the purpose of facilitating the dissociation of lithium perchlorate salt (LiClO4) and thus to enhance Li ion transport. It is a joint theoretical and experimental procedure for evaluating and thus demonstrating the lithium salt dissociation. The procedure implies the correlation between the theoretical pair distribution function (PDF) and conventional X-ray diffraction (XRD) by means of a molecular dynamics (MD) approach. Additionally, we correlated the experimental and theoretical Raman and infrared spectroscopy for vibrational characterization of the lithium salt after dissociation in the polymeric blend. We also performed confocal Raman microscopy analysis to evidence the homogeneity on the distribution of all components and the LiClO4 dissociation in the polymer blend. The electrochemical impedance analysis confirmed that the Li-PAN-PEI blend presents a slightly better lithium conductivity of ∼8 × 10-7 S cm-1. These results suggest that this polymer blend material is promising for the development of novel fluorine-free solid polymer lithium ion electrolytes, and the methodology is suitable for characterizing similar polymeric systems.