Assembly of 4,4'-oxybis(benzoic acid) (H(2)L) with manganese chloride in the presence of 2,2'-biphenyl (2,2'-bpy) affords a new coordination polymer [Mn(3)L(3)(2,2'-bpy)(2)](n) (1), in which the [MnL(2)]n layers are extended by L bridges resulting in a three-dimensional (3-D) coordination framework. The network structure of 1 has unusual (2,6)-connectivity and represents a new type of (8(12) · 12(3))(8)(3) topology. These identical and complementary networks are entangled to generate a self-penetrating supramolecular lattice. Moreover, the fluorescence spectrum of 1 exhibits fluorescent emission in the solution of methanol at room temperature. Electrochemical investigation illustrates the electrochemical properties of the title compound. The structure (C(62)H(40)Mn(3)N(4)O(15))(n) is monoclinic with a = 14.2304(18), b = 17.019(2), c = 25.805(3) Å, α = γ = 90, β = 92.932(2)° and space group C2/c.