Three new Pb(II) complexes of 3‐(2‐pyridyl)‐5‐(4‐methoxyphenyl)‐1,2,4‐triazine (PMPT) ligand with different anionic co‐ligands (1: nitrate, 2: perchlorate and 3: isothiocyanate) in 2 : 1 molar ratios of PMPT ligands and lead(II) salts, [Pb(PMPT)2(NO3)2] (1), [Pb(PMPT)2(ClO4)2] (2) and [Pb(PMPT)2(NCS)2] (3) were synthesized and characterized by physicochemical (CHN, FT‐IR and 1H NMR) and single‐crystal X‐ray diffraction methods. By considering the obtained structural parameters, the lead atoms in 1, 2 and 3 have PbN4O4, PbN4O2 and PbN6 environments, respectively, with holodirected (for 1) and hemidirected (for 2 and 3) coordination spheres. We used electro‐optical Pb(II) complexes family as emitting layer to investigate in fabrication of OLEDs. The current–voltage, luminescence‐voltage characteristics and the absorption (Abs) and electroluminescence (EL) properties of the complex have been investigated. The forester radius, quantum yield, and electroluminescence have been studied.