This study addressed the design and syntheses of diverse ligands, which were then successfully treated with Ni (II) ion to afford a series of nickel complexes. α-Chloroformylarylhydrazine hydrochlorides 6 contain two different functional groups. One is a strong nucleophile, and the other is a good electrophile. Therefore, it can be designed to react with several reagents to obtain diverse derivatives which can be used as ligands for metal complexes. Furthermore, benzimidazole and salicylaldehyde can provide electron donor sites, N and O electron donors, separately. Hence, the starting materials α-chloroformylarylhydrazine hydrochlorides 6 were first treated with 2-(aminomethyl)-benzimidazole (7) to give the corresponding semicarbazides 8. Then, the semicarbazides 8 reacted with various substituted salicylaldehydes 9–11 to afford the desired substituted-salicylaldehyde 2-aryl-4-substituted semicarbazones 12–14, which could coordinate with nickel (II) ion to give the corresponding nickel complexes 15–17.