In this work, new materials based on the blends of polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), chitosan (CS), and polydopamine (PDA) have been prepared. Fourier Transform Infrared Spectra have been conducted to verify the presence of individual components in the composite materials. EDX elemental analysis showed a clear view of the element’s presence in the composite materials, with the maximum values for carbon and oxygen. Atomic force microscopy (AFM) was used to observe the surface topography and measure the surface roughness. In the case of the individual polymers, CS presented the higher value of surface roughness (Rq = 3.92 nm and Ra = 3.02 nm), and surface roughness was found to be the lowest in the case of polyvinyl pyrrolidone (PVP), and it was with values (Rq = 2.34 nm and Ra = 0.95 nm). PVA films presented the surface roughness, which was with the value (Rq = 3.38 nm and Ra = 2.11 nm). In the case of composites, surface roughness was highest for the composite based on PVA, PVP, and CS, which presented the value (Rq = 11.91 nm and Ra = 8.71 nm). After the addition of polydopamine to the polymeric composite of PVA, PVP, and CS, a reduction in the surface roughness was observed (Rq = 7.49 nm and Ra = 5.15 nm). The surface roughness for composite materials was higher than that of the individual polymers. The addition of PDA to polymeric composite (PVA/PVP/CS) led to a decrease in Young’s modulus. The elongation percentage of the polymeric films based on the PVA/PVP/CS/PDA blend was higher than that of the blend without PDA (9.80% vs. 5.68% for the polymeric composite PVA/PVP/CS). The surface of polymeric films was hydrophilic. The results from the MTT assay showed that all tested specimens are non-toxic, and it was manifested by a significant increase in the viability of L929 cells compared with control cells. However, additional studies are required to check the biocompatibility of tested samples.