Six new Europium (III) complexes with ternary and tetrakis structures - Eu(BID)3(PHEN), Eu(MBID)3(PHEN), [Eu(BID)4]−N+(Et)4, [Eu(MBID)4]−N+(Et)4, [Eu(BID)4]−N+(Bu)4, and [Eu(MBID)4]−N+(Bu)4(BID – 2-benzoyl-1,3-indandionate, MBID - 2-(4-methylbenzoyl)-1,3-indandionate and PHEN – 1,10-phenantroline) are synthesized, characterized, and incorporated into poly-N-vinylcarbazole (PVK) and poly methyl methacrylate (PMMA) matrices. Complex structure shows significant effect on thermal properties and emission properties of complexes in solid-state. Used countercations (N+(Et)4or N+(Bu)4) greatly affects complex solubility in solvents, absolute photoluminescence quantum yields and photoluminescence lifetimes in solid-state. Complexes exhibit red-light emission attributed to5D0→7FJ(J = 0–4) transitions of Eu3+ion with moderate to high quantum yields (0.06–0.60), bi-exponential lifetimes and pure red-light CIE chromaticity coordinates (x = 0.670; y = 0.330) in solid-state. Incorporation of synthesized complexes in PVK matrices leads to significant emission intensity and quantum yield decrease. However, doped PMMA films with synthesized complexes exhibit moderate PLQY (0.09–0.14) and longer lifetime values than in solid-state and could show potential application as polymer optical fibers or in OLED's and other devices.