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Understanding the characteristics of nanomaterials in the context of electrode designs for bio‐electrocatalysis is an emerging research direction. Applications for fuel cells, batteries, and biosensors are directly benefited. The objective of this study is to understand the influence of unfunctionalized multiwalled carbon nanotubes (MWNT) in comparison to carboxylated nanotubes (MWNT−COOH) for pi‐pi stacking with 1‐pyrenebutyric acid (Py) and covalent immobilization of bilirubin oxidase (BOD) enzyme toward the resulting oxygen reduction currents. We designed pyrolytic graphite‐edge electrodes modified with MWNT/Py, MWNT−COOH/Py, or only MWNT−COOH for carbodiimide activation and BOD immobilization. The relative increase in surface −COOH groups as we move from MWNT to MWNT/Py to MWNT−COOH/Py modification is voltammetrically estimated. Although the MWNT−COOH/Py displayed the highest relative amount of surface −COOH groups, the oxygen reduction current was the largest for the BOD‐immobilized MWNT/Py electrode than others. Results indicate that unfunctionalized MWNT is the optimal choice for pi‐pi stacking with pyrene linkers and covalent BOD immobilization as biocathode for energy devices. Favorable hydrophobic MWNT surface to interact more closely with the electron‐receiving T1 Cu site of BOD, as opposed to the relatively polar and more defective MWNT−COOH material due to functionalization, is suggested to be one of the underlying factors for the observed electrocatalytic trend. [ABSTRACT FROM AUTHOR]