A new nano-sized lead(II) one-dimensional coordination polymer with Pb⋯F interactions, [Pb(μ-TFPB)2] n (1) [TFPB− =4,4,4-trifluoro-1-phenyl-1,3-butandionate], has been synthesized and characterized by SEM, X-ray powder diffraction, IR spectroscopy and elemental analyses. The single-crystal X-ray data of compound 1 show that the Pb(II) atoms have a hemidirected coordination sphere with an environment of PbO6F2. The presence of a stereo-chemically active lone pair of the lead atom is apparently the reason that the neighboring bridging bond relative to gap of coordination sphere are so long. Therefore arrangement of “TFPB−” ligands suggests a gap or hole in coordination geometry around the lead(II) ions. PbO nanoparticles were obtained by calcination of the nano-sized compound 1 at 600°C.