Polymers play an indispensable role in advanced technological and biomedical applications owing to their tunable physicochemical and electrical properties. Their use spans from aerospace engineering and radiation shielding to medical devices, biosensors, and drug delivery systems. In the present study, thin films of pure and malachite green (MG) doped polyvinyl carbazole (PVK) were prepared using the solution casting technique to investigate the influence of dopant incorporation on their structural, optical, thermal, and electrical properties. The prepared films were characterized by Fourier Transform Infrared (FTIR) spectroscopy, UV–Visible (UV–Vis) spectroscopy, Field Emission Scanning Electron Microscopy (FE-SEM), Energy Dispersive X-ray (EDX) analysis, X-ray Diffraction (XRD), Differential Scanning Calorimetry (DSC), and Atomic Force Microscopy (AFM). Electrical behavior was studied through Thermally Stimulated Discharge Current (TSDC), dielectric, transient current, and conduction measurements. The results revealed that MG doping induces noticeable changes in morphology, crystallinity, and charge transport characteristics of PVK. Enhanced dielectric response, improved surface uniformity, and modified optical absorption indicate potential applications of these films in electronic, optoelectronic, and radiation-resistant devices.