Display omitted •A new tetrameric ligand (TBTP) was synthesized using click chemistry strategy.•Copper(II) with TBTP form 1-D coordination polymer.•1-D coordination polymers present antiferromagnetic behavior.•Oxidation of aniline to azobenzene is catalyzed by the 1D coordination polymer. A novel tetrameric tetraO-((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)-pentaerythritol (TBTP) has been synthesized using click chemistry strategy. TBTP was characterized and used as ligand to form new Cu(II) complexes, forming 1-D coordination polymers. Two square planar complexes were characterized by single-crystal X-ray diffraction, presenting formula Cu(TBTP)Cu(NO3)4 (1) and Cu(TBTP)(NO3)2 (2). In both structures, a cationic 1-D coordination polymer (CP) has been formed. The CP contain a 1:1 Cu(II)/TBTP ratio with four neutral triazole groups coordinating the Cu(II) center, forming a CuN bonds ranging 1.988(2)–2.001(2) Å. The study of the magnetic properties of compounds 1 and 2 pointed to an antiferromagnetic behavior for both compounds, defined by inter- and intra-chain dipolar interactions among their metallic centers. In addition, the complex 1 was found to be an efficient catalyst for selective oxidation of aniline to azobenzene under mild reaction conditions.