A novel macrocyclic ligand containing catechol moieties, 9,10,21,22-tetrahydroxy-7,12,19,24-tetraoxo-2,3,4,5:8,9,10,11:14,15,16,17:20 ,21,22,23-tetrabenzena-1,6,13,18-tetraazacyclotetracosane (H 4 L), was designed and synthesized. For comparison, an acyclic ligand, 1,4-bis(2,3-dihydroxybenzammido)benzene (H 4 L a ), was also synthesized. Their oxovanadium(IV) complexes K(ppn)[VO(L)] and K 2 [VO(L a )] were prepared and characterized by IR, UV-Vis and ESR spectroscopies. The ESR spectra of the complexes measured at 77 K in diethyl sulfoxide-ethanol revealed unusual rhombic characteristics of the complexes, suggesting the coordination geometry of the complexes was distorted square-pyramidal. Based on these data, the complex is proposed to possess a bowl-like structure capped by the VO 2 + moiety with a hydrophobic cavity.