N-salicylidene-o-aminophenol and two of its derivatives bearing either an electron-donating methyl group or an electron-withdrawing Br group were used as ligands for the synthesis of three Ga(III) complexes. The complexes involved the participation of one acetylacetonate and one ethanol or methanol molecule. The geometry of the dianion of the Schiff base in the complexes is planar while photoluminescence data showed that photoluminescence intensity was extensively increased upon complex formation. Complexes emitted ligand-centered luminescence by ligand-centered excitation. Substituent groups broadly modified emission maximum. These substitutions can be exploited to tune light emission by the complex. All three complexes were used for the construction of electroluminescence devices and all emitted electroluminescence. Both photoluminescence and electroluminescence emission was enhanced in the case of substituted Schiff bases.