Using a conventional fast-shuttered laboratory X-ray source in combination with pulsed laser diode modules, the possibilities for undertaking X-ray/laser interaction spectroscopy in wide band-gap luminescent materials are explored. It is shown that in such materials, a variety of X-ray/laser timing sequences can extract complimentary information regarding the charge-carrier trapping, de-trapping and recombination processes. The effects on the luminescence are illustrated for six example materials (YPO4:Ce,Sm, Lu3Al5O12:Pr, Al2O3:C, natural sodium feldspar NaAlSi3O8, cubic BN and type IIa natural diamond). By ramping the temperature from 10 to 320 K during repeated X-ray pump/laser-probe activation cycles, a rapid assessment can be made of the important thermally dependent changes to the charge carrier trapping competition processes.