RationaleThe chemical constituents of traditional Tibetan medicines (TTM) can be identified using high‐performance liquid chromatography and high‐resolution mass spectrometry (HPLC–MS/MS) technique. However, the HPLC–MS/MS technique requires the sample to be pretreated and then separated using the specific liquid chromatography method, which is time consuming. This study developed a ballpoint electrospray ionization (BPESI) technique for analyzing the chemical constituents of Sbyor‐bzo‐ghi‐wang. This technique is a simple and inexpensive method for the rapid identification of the chemical constituents of TTMs.MethodsAfter the important parameters of the homemade BPESI device were optimized, the chemical constituents of Sbyor‐bzo‐ghi‐wang were quickly identified without sample pretreatment. The raw data were converted to mzML file using MSConvert and then identified using SIRIUS 5 software.ResultsThe results showed that 30 compounds were identified from Sbyor‐bzo‐ghi‐wang, namely eight bile acids, six flavonoids, four alkaloids, three amino acids, and nine others. Compared to the ultra‐high‐performance liquid chromatography‐Q/Orbitrap and high‐resolution mass spectrometry (UHPLC‐Q/Orbitrap HRMS) technique, the BPESI technique identified almost similar types of compounds and also a comparable number of compounds.ConclusionsCompared with the traditional HPLC–MS/MS methods, the BPESI technique does not require complex sample pretreatment and subsequent chromatographic separation steps; also it consumes a small quantity of samples. Therefore, BPESI can be used for the qualitative analysis of the chemical constituents of Sbyor‐bzo‐ghi‐wang.