Four new Pr(III) mononuclear complexes of formula [Pr(ntfa)3(MeOH)2] (1), [Pr(ntfa)3(bipy)2] (2), [Pr(ntfa)3(4,4′-Mt2bipy)] (3) and [Pr(ntfa)3(5,5′-Me2bipy)] (4), where ntfa = 4,4,4-trifuoro-1-(naphthalen-2-yl)butane-1,3-dionato(1-), 5,5′-Me2bipy = 5,5′-dimethyl-2,2′-dipyridine, 4,4′-Mt2bipy = 4,4′-dimethoxy-2,2′-dipyridine, have been synthesized and structurally characterized. The complexes display the coordination numbers 8 for 1, 3 and 4, and 10 for 2. Magnetic measurements of complexes 1–4 were consistent with a magnetically uncoupled Pr3+ ion in the 3H4 ground state. The solid state luminescence studies showed that the ancillary chelating bipyridyl ligands in the 2–4 complexes greatly enhance the luminescence emission in the visible and NIR regions through efficient energy transfer from the ligands to the central Pr3+ ion; behaving as “antenna” ligands.