The silicates Ca3Sc2Si3O12, Ca3Y2Si3O12 and Ca3Lu2Si3O12, both undoped and doped with Pr3+ ions, have been synthesized by solid-state reaction at high temperature. The luminescence spectroscopy and the excited state dynamics of the materials have been studied upon VUV and X-ray excitation using synchrotron radiation. All doped samples have shown efficient 5d–4f emission upon direct VUV excitation of 5d levels, but only Ca3Sc2Si3O12:Pr3+ shows luminescence upon interband VUV or X-ray excitation. The VUV excited emission spectra of Ca3Y2Si3O12:Pr3+ and Ca3Lu2Si3O12:Pr3+ show features attributed to emission from two distinct sites accommodating the Pr3+ dopant. The decay kinetics of the Pr3+ 5d–4f emission in Ca3Sc2Si3O12:Pr3+ upon VUV excitation across the band gap are characterized by decay times in the range 25–28 ns with no significant rise after the excitation pulse. They appear to be faster upon X-ray irradiation than for VUV excitation. Weak afterglow components are attributed to defect luminescence