A novel nickel(ii) complex, [Ni(2,2'-bpy)3](H2SBTC)(H2O)5 (1) (2,2'-bpy = 2,2'-bipyridyl), was synthesized based on [Ni(2,2'-bpy)3]2+ discrete units and a partially deprotonated sulfonate-carboxylate ligand of H4SBTC (5-sulfonyl-1,2,4-benzentricarboxylic acid). The adjacent [Ni(2,2'-bpy)3]2+ cationic units were connected to H2SBTC2- anions by hydrogen bonds to form a one-dimensional (1-D) chain. The 1-D chains were further linked using hydrogen bonds from free water molecules and H2SBTC2- anions to generate a two-dimensional (2-D) plane structure. The proton conductivity of 1 reaches 1.3 × 10-4 S cm-1 at 318 K, 98% RH. Furthermore, hybrid membranes composed of polyvinyl alcohol (PVA) and 1 as fillers were prepared with different mass percentages. The proton conductivity of 1@PVA-5 was found to be 1.6 × 10-3 S cm-1 at 313 K and 98% RH. The large number of alcoholic hydroxyl groups in PVA promote the resulting conductivity.