Two new metal complexes formulated as [Mg(L)2(H2O)2]·H2O (1) and [Zn(L)2(H2O)2]·0.5H2O (2), where HL = 5-hydroxyflavone (primuletin), have been synthesized and characterized by elemental and thermal analyses, molar conductance, IR, UV-Vis, 1H- and 13C-NMR, fluorescence and mass spectra. In solid state, complexes had shown higher fluorescence intensities comparing to the free ligand, and this behavior is appreciated as a consequence of the coordination process.