Four new terbium(III) ternary complexes, [Tb(fod)3(indazole)] (1), [Tb(fod)3(tptz)] (2), [Tb(fod)3(impy)] (3) and [Tb(fod)3(tppo)2] (4) with 6,6,7,7,8,8,8‐heptafluoro‐2,2‐dimethyl‐3,5‐octanedione, (Hfod) and N and O donors are synthesized and structurally characterized. The photoluminescence of the complexes are studied in solid, chloroform solution and thin PMMA hybrid films (PMMA is a poly(methyl methacrylate)). The ligand‐based emission is dominant in solution of 3 and 4. The effect of ancillary ligands on the photoluminescence of terbium(III) ion is investigated. The mechanism of energy transfer is discussed and correlates the luminescence of acceptor terbium ion with the triplet state energy level of donor ligands. Among the four complexes studied, the luminescence from 1 is most intense followed by 2, 4 and 3. The Commission International de I’Eclairage (CIE) color coordinates of these complexes are calculated and presented. The complexes 3 and 4 show intraphase color tuning when excited under different UV wavelengths. The emission color of [Tb(fod)3(tppo)2] (4) changes from pure blue to turquoise green via almost pure white under 360, 328 and 280 nm UV excitation wavelengths respectively. The [Tb(fod)3(impy)] (3) show similar results. The complex [Tb(fod)3(tptz)] (2) displays interphase color tuning from yellow (solution) to turquoise green (solid) and fascinatingly incorporation of complex in PMMA polymer generates white light under same excitation wavelength (360 nm).