Highly luminescent ZnS∶Au, Cu X-ray phosphor fine particles synthesized by hydrothermal method is reported for the first time and its photoluminescence (PL) and X-ray excited luminescence (XEL) properties were studied in detail. With direct hydrothermal treatment at 200 ℃ for 12 h, the average gain size of samples is about 15 nm; the synthesized sphere-like nanocrystals with well dispersity and narrow gain size distribution show cubic structure. After baking in argon at 1 000 ℃ for 1h the sample agglomerate size is about 1-2 μm and the roughly spherical fine particles show pure hexagonal structure. The PL and XEL spectra of all the samples show a broad emission band and an intense emission band in the range of 400-600 nm. The maximum XEL intensity of sample directly synthesized by hydrothermal treatment was observed when Cu/Zn and Cu/Al were 3×10-5 and 2, respectively. In this condition, the strongest PL emission was observed for the direct synthesized sample being further baked in argon at 900 ℃ for 1 h and the PL peak was centered at about 529 nm. The strongest XEL emission was observed for the direct synthesized sample being further baked in argon at 1 000 ℃ for 1h and the XEL peak was centered at about 445 and 513 nm, respectively. In the meantime, the XEL intensity increased about ten times compared with that directly synthesized without baking. The difference between PL and XEL spectra is due to its different excitation mechanism. The luminescence mechanism and different excitation mechanism of PL and XEL were discussed. The red shift of XEL spectrum with directly synthesized sample was observed with increasing the Cu/Zn. The reason can also be explained by the luminescence mechanism and excitation mechanism of XEL.