Treatment of N,N′-bis(4-pyridylmethylene)-1,5-naphthalenediamine (L) with Pb(OAc)2/KBr, Cu(acac)2, and Cu(OAc)2 afforded three new coordination polymers [Pb(μ-L)(μ-Br)2]n (1), [Cu(μ-L)(acac)2]n (2), and [Cu2(μ-L)(μ-OAc)4]n (3). These coordination polymers have been structurally characterized by single crystal X-ray diffraction. Compound 1 has a 2D sheet structure in which the lead(II) centers are bridged by both L and bromide ligands. Compound 2 adopts a 1D neutral coordination chain and consists of bis(2,4-pentanedionato) copper(II) units connected by rigid bridging L ligands. The structure of compound 3 also adopts a 1D neutral coordination chain in which two copper centers are connected through four acetate groups to form a Cu(OAc)4Cu paddle-wheel-type cage between two bridging L ligands. The FT-IR spectra, thermal behavior and photoluminescence properties of these coordination polymers have also been investigated.