A new 1D chained Ca(II) coordination polymer—namely, [CaL2(H2O)2]n (HL = 3,5-bis(4-pyridylmethoxy)benzoic acid)—was synthesized though the reaction of Ca(ClO4)2·4H2O, 3,5-bis(4-pyridylmethoxy)benzoic acid and NaOH in H2O/CH3CH2OH (v:v = 1:2) solution. Its structure was determined by elemental analysis, infrared spectrum, and single-crystal XRD. Structural analyses show that each Ca(II) ion is eight-coordinated by six oxygen atoms of four 3,5-bis(4-pyridylmethoxy)benzoate ligands and two oxygen atoms of two coordinated H2O molecules to form a square-antiprismatic CaO8 polyhedron. The Ca(II) complex displays a 1D chained structure constructed by the bridging effect of the bidentate carboxyl group of 3,5-bis(4-pyridylmethoxy)benzoate ligand. The catalytic activity of the Ca-complex was tested for the preparation of propargylamine in the A3 coupling reaction.