Investigating the distribution of different Zn species on Zn-containing zeolite catalysts is crucial for identifying the active sites and establishing the relationship between the catalyst’s structure and its activity in the process of ethylene aromatization. By utilizing X-ray absorption near edge spectra (XANES) of various reference samples, this study employed linear combination fitting (LCF) analysis on XANES spectra of real samples to accurately measure the changes in the distribution of Zn species in Zn-containing HZSM-5 zeolites under different Zn sources and loadings. The results showed that ZnOH+, ZnO clusters, and ZnO crystalline structures coexist in Zn/HZSM-5 catalysts prepared through physical mixing and incipient wet impregnation methods. A similar trend was observed for catalysts prepared using different methods, with an increase in Zn content resulting in a decrease in the proportion of ZnOH+ and a significant increase in the amount of larger ZnO crystals. Furthermore, ZnO clusters were confined within the zeolite pores. The findings of this study established a direct correlation between the amount of ZnOH+ determined through LCF analysis and both the rate of hydrogen production and the rate of aromatics formation, providing strong evidence for the catalytic role of ZnOH+ as an active center for dehydrogenation, which plays a key role in promoting the formation of aromatics. The method of LCF analysis on XANES spectra allows for the determination of the local structure of Zn species, facilitating a more precise analysis based on the distribution of these species. This method not only provides detailed information about the Zn species but also enhances the accuracy of the overall analysis.