We describe the preparation of three-dimensional hierarchical twin-scale inverse opal (ts-IO) electrodes for dye-sensitized solar cells (DSSCs). The ts-IO TiO(2) structure was obtained from a template fabricated via the assembly of mesoscale colloidal particles (40-80 nm in diameter) in the confined geometry of a macroporous IO structure. The photovoltaic properties of ts-IO electrodes were optimized by varying the layer thickness or the size of mesopores in the mesoscale colloidal assembly. Electron transport was investigated using impedance spectroscopy. The result showed that due to the competing effects of recombination and dye adsorption, the maximum efficiency was observed at an electrode thickness of 12 μm. The electrodes of smaller mesopores diameters yielded the higher photocurrent density due to the decrease in the electron transport resistance at the TiO(2)/dye interface. A maximum efficiency of 6.90% was obtained using an electrode 12 μm thick and a mesopore diameter of 35 nm.