Highly ordered, and conductive inverse opal arrays were made with silica and subsequently coated with tin-doped indium oxide (ITO) via atomic layer deposition (ALD). We demonstrate the utility of the resulting mesostructured electrodes by further coating them with nickel oxide via ALD. The NiO-coated arrays are capable of efficiently electrochemically evolving oxygen from water. These modular, crack-free, transparent, high surface area, and conducting structures show promise for many applications including electrocatalysis, photocatalysis, and dye-sensitized solar cells.