Five new NiII/3-sb/2,2′-bipy and NiII/3-sb/phen complexes, {[Ni(3-sb)(phen)(H2O)2]·H2O}n (1), [Ni(3-sb)(phen)2(H2O)]·H2O (2), [Ni(phen)3]·2(3-Hsb)·10H2O (3), {[Ni(3-sb)(2,2′-bipy)(H2O)2]·H2O}n (4), and [Ni(2,2′-bipy)3]2·(3-Hsb)·3(NO3)·9H2O (5) [3-sb = 3-sulfobenzoate dianion; 2,2′-bipy = 2,2′-bipyridine; phen = 1,10-phenanthroline], have been synthesized and structurally characterized. The molecular structures of complexes 1 and 4 are 1-D polymers in which the 3-sb ligands bis-monodentately coordinate to the NiII ions. Complex 2 is a monomer. Complexes 3 and 5 are cation–anion species in which the 3-Hsb− ligands are non-coordinating. These complexes containing interesting supramolecular assembly interactions: hydrogen-bonding interactions, π⋯π stacking interactions, and other weak interactions. The stability of complexes 3 and 5 from their TG analyses is higher than that of others, indicating that the host–guest assembly enhances the stability of the solid state. Interestingly, the catalytic experiments showed that complex 3 is the best catalyst among these nickel complexes for the oxidation reaction of methyl phenyl sulfide due to 3-D host–guest supramolecular assembly and stacking effects.