The Djebel Gustar Zn-Pb deposit in northeastern Algeria is one of many carbonate-hosted base metal deposits in the Atlas metallogenic province of North Africa. The sphalerite in this deposit occurs in five distinct types that differ in texture, mineral assemblage, chemical composition, and UV photoluminescence signature. Detailed investigation of trace elements by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) showed that the sphalerite is significantly enriched in the critical metal Ga. The trace element concentrations of the different sphalerite types correlated well with their photoluminescence color; with Mn2+ (orange-yellow), Cu+ (green), and Ga3+ (red) being the dominant activators. We suggest that the Ga enrichment in the Djebel Gustar deposit is the result of formation conditions that include the mixing of a Cl-rich fluid carrying mainly Zn and Pb with a more reduced and Cl-poor fluid containing considerable organic matter and/or calcite with adsorbed Ga(OH)3. This Ga was subsequently incorporated into sphalerite, rather than forming a stoichiometric Ga phase. Furthermore, our study demonstrates that UV photoluminescence of low Fe sphalerite has the potential to become a simple and affordable tool for preliminary characterization of sphalerite ores in mining and exploration with respect to critical elements such as Ga.