Hybrid materials are increasingly demonstrating their utility across several optical, electrical, and magnetic applications. Cu(I) halide-based hybrids have attracted attention due to their strong luminescence in the absence of rare-earths. Here, we report three Cu(I) and Ag(I) hybrid iodides with 1,5-naphthyridine and additional triphenylphosphine (Ph3P) ligands. The compounds are built on (Cu/Ag)-I staircase chains or on a rhomboid Cu2I2 dimer and display intense and tunable luminescence. Replacing Cu with Ag, and adding the second kind of organic ligand (Ph3P) tunes the emission color from red to yellow and results in significantly enhanced quantum yield. Density functional theory-based electronic structure calculations reveal the separate effects of the inorganic module and organic ligand on the electronic structure, confirming that bandgap, optical absorption, and emission properties of these phosphors can be systemically and deliberately tuned by metal substitution and organic ligands cooperation. The emerging understanding of composition-structure-property relations in this family provides powerful design tools toward new compounds for general lighting applications.