The vacuum ultraviolet spectroscopic properties of GdOCl:Re3+ (Re3+=Ce3+, Tb3+, Eu3+, and Dy3+) are investigated in detail for the first time. The host absorption band is determined to be around 179nm, and the f–d transition bands as well as the charge transfer bands are assigned. Upon 179nm excitation, Re3+ (Re3+=Ce3+, Tb3+, Eu3+, Dy3+) ions shown their characteristic emissions. Energy transfers from Gd3+ to Re3+ ion were observed. A broad band ranging from 350 to 400nm corresponding to the d–f transition of Ce3+ is observed. Eu3+ has typical red emission with the strongest peak at 620nm; Tb3+ shows characteristic transition of 5D3,4→7Fj, and its spin-forbidden and spin-allowed f–d transitions in VUV region are calculated with Dorenbos’ equations, these calculated values agree well with the experimental results. Dy3+ presents yellow emission (4F9/2→6H13/2) with the strongest peak at 573nm.