Mechanoluminescence is observed in oxynitride glass-ceramics from the BaO-SiO2-Si3N4 chemical system, doped with Eu and Ho. Light emission was investigated by means of uniaxial compression experiments on disks and parallelepipedic bars with constant loading rates ranging from 0.3 to 300 MPa s−1 up to about 500 MPa. In agreement with previous reports on SrAl2O4-based materials [Dubernet et al., Appl. Phys. Lett. 107, 151906 (2015) and Dubernet et al., Sci. Rep. 10, 19495 (2020)], the mechanoluminescence intensity is found proportional to the mechanical power. Nevertheless, in contrast with SrAl2O4, no gain in the intensity is observed at the onset of the unloading stage, but a drop of the photoluminescence intensity during unloading. This stems from different electron trapping populations and associated energy levels for the Ba4Si6O16 phase (the dominant crystallized phase in the present glass-ceramics), which are discussed in light of density functional theory calculations.