Automotive glasses are important forensic evidence often recovered from crime scenes. Black ceramic prints on automotive glasses contains various elements in high concentrations. A portable X-ray fluorescence spectrometer (pXRF) allows an instant and nondestructive analysis of various elements. In this study, the Bruker Tracer 5 g was used as the pXRF equipment. The NIST SRM612 glass standard was used to determine the limit of detection (LODs) of a pXRF and its optimal conditions. The acceleration voltages of 15, 30, and 50 kV were appropriate for measuring Si K α (1.740 keV)-Ni K α (7.473 keV), Cu K α (8.042 keV)-Pb L α (10.552 keV), and after Bi K α (10.839 keV), respectively. The pXRF was used to compare 37 black ceramic prints on automotive glasses from the known source. The samples were divided into two groups: the Pb type and the Bi type. The samples were compared in pairs. The most appropriate and effective indicators for discriminating between the Pb and Bi type of black ceramic prints on automotive glasses were Zr K α /Pb L α and Cu K α /Cr K α for the Pb type, and Zr K α /Bi L α and Cu K α /Cr α for the Bi type, respectively. The samples were compared with other elements detected by pXRF to further discriminate them. 98.9% of all pairs were successfully discriminated. Results showed that black ceramic prints on automotive glasses are able to be discriminated by pXRF.