Polymer composite films based on polycaprolactone/polyvinylchloride (PCL/PVC) blend containing CoCl2 were created using the low-cost technique (solution casting). The current study was based on synthesizing PCL/PVC (50/50 wt%) composites using CoCl2 as a filler in various weight ratios (0, 2, 4, 8, and 16 wt%). Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were used to provide more light on the structural change brought about by the doping of CoCl2 at varying amounts in the polymeric matrix. XRD spectra showed that the two main humps of the PCL/PVC blend were inhibited largely, and many sharp peaks appeared, depicting the reduction of the crystallinity degree and the presence of CoCl2 crystallites within the prepared composite films. With the use of SEM images, a uniform dispersion of the CoCl2 filler into the polymeric matrix at the low CoCl2 wt.% CoCl2 was seen to be attached to the polymeric chains and to diffuse through the amorphous regions, producing aggregates between the polymeric chains, as the CoCl2 levels increased. UV–Vis spectroscopy showed that the optical parameters of samples were mainly improved, and the optical band gap values were considerably decreased by increasing the wt.% of CoCl2 filler. Also, the theoretical Wemple-DiDomenico model had been applied to gag the refractive index , the dispersion energy (Ed) and the oscillation energy (Eo). The VSM curves indicated the ferromagnetic features of PCL/PVC/CoCl2 films. These results will widen the applications of PCL/PVC/CoCl2 composites in optoelectronics, magnetic storage and energy storage devices.