We report on the electrodeposition of 3D macroporous vanadium oxide inverse opals and binary inverse opals on transparent conducting oxide substrates and stainless steel and thermally oxidized stainless steel substrates. The electrodeposition follows a diffusion limited growth mode to form 3D porous crystalline V2O5 after removal of a colloid photonic crystal template of self-assembled polystyrene spheres. Inverse opals were grown using spheres ranging in diameter from 0.5 μm to 6 μm, and binary inverse opals were also electrodeposited using binary mixtures of sphere sizes. We demonstrate that the ionic diffusion that leads to growth has charge-to-mass Coulombic efficiency ranging from 60–90%, depending on the voltage used. Additionally, the tortuosity in ionic diffusion through the opal to the substrate is significantly increased when large sphere diameter templates and binary opal templates are used. Analysis of the contribution of true substrate active area and the influence of template structure on ionic diffusivity confirms that inverse opal growth is dictated by the size of opal spheres, interstitial void clogging by smaller spheres in binary opals, and the conductivity of the substrate active area. The crystallinity of the inverse opal is consistent and a function of applied voltage, and attains phase pure orthorhombic V2O5.