Two novel mixed-ligand complexes of lead(II), [Pb(Cup)₂(Phen)]₂](DPE) (1) and [Pb(Cup)(ONO₂)(Phen)] (2) (Cup = cupferronato, Phen = 1,10-phenanthroline, and DPE = 1,2-di(4-pyridyl)ethylene), were synthesized in the presence of common bridging ligands which are usually used in synthesis of lead(II) coordination polymers as well as utilization of Cup and Phen as O,O′- and N,N′- chelates, respectively. Structural features of 1 and 2 in solution were investigated by ¹H and ¹³C NMR experiments. The accurate assignment of these signals was inferred from a series of ¹H–¹H COSY, ¹H–¹³C HSQC, and ¹H–¹³C HMBC spectra. The solid-state structures of 1 and 2 were also investigated via single crystal XRD. By considering the obtained structural parameters, the coordination of 1 is hemidirected while 2 is suggested to be holodirectional. Additionally, complex 1 consist of dimers which are further …