The qualitative analysis of the elemental compositions of thirty samples of car paints (original varnish and currently applied in car paint workshops) was carried out using two physicochemical methods: X-ray fluorescence spectrometry (XRF) and neutron activation analysis (NAA). The Amptek Experimenter’s XRF Kit was used for XRF studies. The neutron irradiation for NAA was carried out at Research Reactor Maria of the National Centre for Nuclear Research in Świerk. It was found that the elemental composition between the samples differs significantly. Only one pair of varnish samples tested with the XRF method showed the same elemental composition. The NAA method fully differentiated all samples. A quantitative comparison of the sensitivity of both methods to differentiate the samples was performed. NAA method was found to be more sensitive compared to the XRF technique.