Several new coordination polymers (CPs), [MnIJ4, 2 (H 2 O) 2 ] n (1), [Zn(4, 4,benzoic acid N-oxide), have been successfully synthesized and characterized by elemental analyses, IR spectroscopy, thermogravimetric analysis and single crystal X-ray diffraction. Structural analysis shows that complex 1 features a two-dimensional (2D) layer with a 6 3 topology. Complexes 2 and 3 present a 2D layer architecture with a 4•8 2 topology. Complex 4 presents an unusual onedimensional (1D) chain constructed with linear trinuclear secondary building units (SBUs). Complex 5 has a zero-dimensional (0D) structure which is further connected to form a 2D supramolecular network through O-H⋯O hydrogen bonding. Complex 6 exhibits a 2D layer which is further connected by π⋯π interactions to produce a three-dimensional (3D) supramolecular framework with 1D opening channels. Moreover, as an anode material, complex 6 exhibits a relatively high irreversible capacity of about 860 mA h g −1 in the first discharge process and a reversible lithium storage capacity of up to 405 mA h g −1 at 100 mA g −1 after 100 cycles. The observation of good storage performance demonstrates that CPs are a prospective class of electrode materials for lithium ion batteries (LIBs).