Direct electron transfer (DET)-type bioelectrocatalytic waves of bilirubin oxidase (BOD)-catalyzed O 2 reduction and [NiFe] hydrogenase (H 2 ase)-catalyzed H 2 oxidation are very small and un-detectable using glassy carbon (GC) electrodes, respectively; however, clear catalytic waves are observed when the enzymes are adsorbed on Ketjen black-modified GC (KB-GC) electrodes, in which KB provides mesopores for DET-type bioelectocatalysis. To explain the phenomena, we focus on the curvature effect of mesoporous structures on long range electron transfer kinetics and simulate steady-state voltammograms catalyzed by model redox enzymes adsorbed with a random orientation on planar and mesoporous electrodes based on a three-dimensional model. In the simulation, we assume a spherical enzyme with a radius of r, an active site located at a certain distance from the center of the enzyme, and a spherical pore with a radius of R p in mesoporous electrodes in which the enzyme is trapped and adsorbed. The simulation reveals that mesoporous electrodes provide platforms suitable for DET-type bioelectrocatalysis of enzymes when R p becomes close to r. Such curvature effects of mesoporous electrodes become especially notable for larger sized enzymes. Furthermore, the simulation reproduces the experimental data of BOD-and H 2 asecatalyzed DET-type waves by considering the crystal structures of the enzymes. This work will open a route to improve the kinetic performance of the DET-type bioelectrocatalysis that has become very important in its practical application to a variety of bioelectrochemical devices.