To investigate the effect of the sites of S-atoms in thiophene carboxylates on the structures of coordination polymers, two thiophene-mono-carboxylic acids (2-Htpc = thiophene-2-carboxylic acid and 3-Htpc = thiophene-3-carboxylic acid) and a fluorescent active semi-rigid amide [N,N′-bis(3-methyl pyridine-3-yl)-2,6-naphthalenediamide (L)] were selected to combine with electrochemically active metal ions of Ni(II), and two new coordination polymers (CPs), namely [Ni0.5(L)0.5(2-tpc)](H2O)]∙1.5H2O (1) and [Ni0.5(L)0.5(3-tpc)](H2O)]∙1.5H2O (2), were obtained through traditional hydrothermal methods. The single-crystal X-ray diffraction analyses of the two CPs show that there are similar zigzag chains with the crossed-stacking modes. The two CPs can act as multifunctional electrochemical sensors to detect NO2−, chloramphenicol, and L-ascorbic acid (AA) and fluorescent recognition of Fe3+ and Cr2O72−. The detection limits of 1 were 1.08 × 10−6, 1.18 × 10−4, and 1.06 × 10−4 for AA, Fe3+, and Cr2O72−. The corresponding values of 2 were 1.43 × 10−6, 2.06 × 10−4, and 2.06 × 10−4. Two Ni(II) coordination polymers showing the same crossed-stacking modes display electrochemical and fluorescent sensing properties for metal ions and anions.