High-resolution X-ray absorption measurements (with an accuracy of ± 0.3 eV) of ZnSO4 (aq) were performed with ultrafast selected energy X-ray absorption spectroscopy (USEXAS) using a laser-driven tungsten target X-ray source. The results were used to determine the absolute spectral positions of characteristic emission lines. By comparing these positions to those predicted for the line emission from tungsten of different oxidation states using the Dirac-Fock formula, the tungsten species responsible for ultrafast hard X-ray generation were found to be tungsten atoms. This finding provides the first direct evidence to support the mechanism of X-ray generation via high-energy electrons interacting with tungsten atoms in the solid target.