This Letter reports a comparative study of the luminescence from pristine and Cr-doped MgAl2O4 spinel induced by different excitation mechanisms: photoluminescence (PhL), thermoluminescence (ThL) and Photo-Induced Chemisorption Luminescence (the PhICL phenomenon) to understand the mechanism of PhICL emission. Cr-doping alters the major pathway of physical relaxation through a luminescence pathway: quenching of the luminescence associated with intrinsic defects and appearance of the luminescence from Cr3+-states. The similarity between ThL and PhICL spectra suggest the mechanism of the PhICL phenomenon is due to electron transfer from the surface to the emission centers of luminescence;an energy transfer pathway is not precluded.