Metal halide perovskites have been extensively studied recently by virtue of their extraordinary luminescence characteristics. However, they still suffer from severe stability issues, and contain a toxic metal lead. Here, single crystals of (PEA)4Cu4I4, a lead-free orange-red-emitting organic-inorganic copper-halide compound with a photoluminescence quantum yield (PLQY) of 68%, were synthesized via a simple solvent vapor diffusion process with commercially-available phenylethylamine (PEA) as a ligand. The crystals show superior stability to perovskites with retaining 60% of their initial photoluminescence (PL) intensity after 60 days in water, which is due to the hydrophobic nature of PEA and the stable Cu-N bonds. Phase transition is found to take place upon lowering the temperature, which causes a redshift of the PL peak. The emission band is identified to be associated with triplet cluster-centered (CC) excited states because of their shortened Cu-Cu distances, excitation-independent PL and long PL lifetime. In addition, micron-sized oleic acid capped (PEA)4Cu4I4 particles were developed by a hot-injection method, and they possess similar stability to that of bulk crystals. A monochrome LED was further fabricated by employing the as-prepared micron-sized particles as phosphors, demonstrating their potential for optoelectronic applications.