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Immobilization of a catalytically active metal complex onto an electrode surface in highly dispersed form is crucial to assure high catalytic activity observed in solution. In this report, mononuclear CoII chlorin complexes were successfully immobilized on a conductive metal-oxide electrode by using electron conducting molecular wires comprising phenylene–ethynylene-based π-conjugation covered by a linked permethylated α-cyclodextrin to enhance electrocatalysis for selective two electron reduction of molecular oxygen to hydrogen peroxide. First, the rotaxane-encapsulation effect of the molecular wire on electron transfer was examined by the comparison of electrochemical behaviors of ferrocene (Fc) molecules immobilized on an ITO substrate using the molecular wires with or without rotaxane encapsulation. Then, electrodes were modified with metalloporphyrinoids, i.e., RhIII(OEP)Cl (OEP = 2,3,7,8,12,13,17,18-octaethylporphyrin) and CoII chlorin through coordination with the molecular wires with pyridine moieties at the end. The electrocatalytic O 2 reduction was performed with CoII chlorin immobilized on an electron-conductive metal-oxide substrate by molecular wires. The turnover frequency for H 2 O 2 production using the CoII chlorin coordinated by molecular wires with rotaxane encapsulation was 331 ± 75, which is significantly higher than that of 82 ± 8 obtained for CoII chlorin immobilized by that without rotaxane encapsulation. These results clearly indicate that the molecular wires with rotaxane encapsulation are beneficial for CoII chlorin complexes to exhibit high electrocatalytic activity and selectivity to H 2 O 2. [Display omitted] • Efficient electron transfer from metal-oxide electrodes to a metal complex was realized by using molecular wires. • Molecular wires with rotaxane encapsulation was suitable for efficient electron transfer and maintaining monomeric structure. • Molecular wires with pyridyl group at the end can coordinate to various metal complexes including porphyrinoids. • Molecular wires enable the cobalt chlorine complex to maintain monomeric structure suitable for H 2 O 2 production. [ABSTRACT FROM AUTHOR]