Photoemission yield spectroscopy in air (PYSA) was applied for the characterization of catechins in water in ambient conditions. According to the results of measurements on aqueous solutions of epigallocatechin gallate (EGCg) of various concentrations, the photoemission yield is almost proportional to the concentration of EGCg. Contrarily, the threshold energy of photoemission, E_PET, is almost constant at 5.46 ± 0.02 eV. Moreover, we measured aqueous solutions of epicatechin (EC), epigallocatechin (EGC), and epicatechin gallate (ECg). The values of E_PET of EC, EGC, ECg were estimated to be 5.72 ± 0.02, 5.68 ± 0.01, and 5.45 ± 0.02 eV, respectively, and a dependence on the molecular structure was found. Furthermore, changes in the photoemission yield spectra of heated EGCg were well explained by molecular orbital calculations on the basis of an assumption of epimerization.