Hexa-methyl-phospho-ramide (hmp), tetra-thio-tungstate, silver sulfide and cerium nitrate were self-assembled to form a one-dimensional anionic [Ag(4)W(4)S(16)](n) (4n-) chain in the title compound, {[Ce(NO(3))(2)(C(6)H(18)N(3)OP)(4)][AgWS(4)]}(n). The asymmetric unit contains four crystallographically independent [Ce(hmp)(4)(NO(3))(2)](+) cations, which leads to a one-dimensional polymeric anionic chain having a tetra-valent [W(4)S(16)Ag(4)] repeat unit. Each central Ce atom is coordinated by eight O atoms from two chelating nitrate and four hmp ligands, which gives rise to a distorted square-anti-prismatic structure. The polymeric chain with average W-Ag-W and Ag-W-Ag bond angles of 163.75 and 151.84°, respectively, presents a distorted linear configuration. The title complex with a non-centrosymmetric structure, is analogous to the Yb, Y, Eu, Nd, La and Dy isomorphs, which exhibit centrosymmetric structures.