Poly (N-vinyl-carbazole) (PVK) thin films doped with bromine has been studied by scanning electron microscopy, X-ray diffraction, infrared absorption, X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR), optical transmission (visible, near ultra violet) and conductivity measurements. The polymer has been doped at room temperature and at 373 K. It is shown by ESR, XPS and optical measurements that a charge transfer complex (CT-complex) is formed between PVK and Br. However, if some bromine acts as dopant of the polymer there is another bromine contribution, which corresponds to bromine covalently bonded to PVK and some only adsorbed. It is also shown by ESR that there is not only polymer doping by bromine but also some partial polymer degradation. Therefore, it can be said that the optimum doping condition of PVK thin films with bromine has been shown to be room temperature post-doping.