The crystal structure of the title calcium complex, [Ca(C(8)H(11)NO(5)PS)(2)](n), is composed of a polymeric chain, which is formed due to two bridging sulfonyl groups linking Ca(II) ions in a O-S-O-Ca manner. Thus, the coordination environment of the Ca(II) ions is composed of six O atoms belonging to the phosphoryl and sulfonyl groups of two chelate rings and two additional O atoms of two bridging sulfonyl groups. The coordination polyhedron of the central atom (2 symmetry) has a distorted octa-hedral geometry.