The detection of neutral biogenic amines plays a crucial role in food safety. Three new heterobimetallic Ru(II)-Ln(III) donor-acceptor complexes, KPrRu, KNdRu, and KSmRu, K{[Ru((II))((t)Bubpy)(CN)4]2-Ln((III))(H2O)4} (where (t)Bubpy = 4,4'-di-tert-butyl-2,2'-bipyridine), have been synthesized and characterized. Their photophysical and X-ray crystallographic data were reported in this study. These complexes were found to be selective for biogenic amine vapors, such as histamine, putrescine, and spermidine, with a detection limit down to the ppb level. The sensitivities of these complexes to the amines were recorded as ~log K = 3.6-5.0. Submicron rods of the complexes, with a nanoscale diameter and microscale length, were obtained through a simple precipitation process. Free-standing polymeric films with different degrees of porosity were fabricated by blending the submicron rods with polystyrene polymer. The polymer with the highest level of porosity exhibited the strongest luminescence enhancement after amine exposure. Real time monitoring of gaseous biogenic amines was applied to real fish samples (Atlantic mackerel) by studying the spectrofluorimetric responses of the Ru(II)-Ln(III) blended polymer film.