A new homodinuclear [Eu(btfa)3]2bpm[1] complex was synthesized, characterized and successfully employed as an emitting layer (EML) to fabricate red-OLEDs. Single crystal X‐ray diffraction analysis reveals that the two Eu(III) ions in the complex are eight coordinate, where the bpm behaves as a tetra-dentate N-donor ligand bridging the two Eu(III) ions symmetrically with distorted square antiprism (SAP, D4d) coordination geometry. The complex exhibited bright red emission with (CIE)x,y color coordinates = 0.670; 0.330 with an absolute photoluminescence quantum yield (PLQY) of 54.4% and sensitization efficiency (ηsen) of 76.73%. Finally, the complex was used as an EML to fabricate single- and double- emitting layer (EML) red-emitting OLEDs. Double-EML device at the optimum doping concentration of 4.0 wt% displayed impressive EL performances with brightness (B) = 812 cd/m2, maximum current efficiency (ηc) = 3.97 cd/A, maximum power efficiency (ηp) = 3.89 lm/W, and external quantum efficiency (EQE) = 2.8% at very low Vturn-on = 3.2 V having a (CIE)x,y = 0.662, 0.321, close to the standard red color recommended by NTSC (0.67, 0.33).