We have performed low-temperature (8K) photoluminescence (PL) measurements on 71 natural and 12 high-pressure-and-high-temperature (HPHT)-treated type IIa diamonds. The GR1, NV 0 , NV − , H4, and H3 defect center PL signals are compared. Some distinct differences in the PL lineshape, intensity, and appearance of side-band PL signals are observed. Furthermore, we processed 6 of the natural diamond samples with the HPHT treatment to investigate the effect of the treatment on the PL spectrum. By systematically analyzing the differences in the PL spectra, we developed a scheme to discriminate natural and HPHT-treated diamonds with 99% validity.