Hierarchically ordered porous materials, as often presented in nature, have drawn intense attention owing to the drastically enlarged surface area, the defined multiscale porous structure, and the new route of introducing additional functionality. This class of materials present significant potential in the fields of molecular separation, catalysis, micro-reactors, tissue engineering, photonic bandgap (PBG) materials. Binary colloidal crystal, a binary crystal structure formed by two sizes of colloidal particles, has proven to be an excellent template for fabricating hierarchically ordered porous materials. More importantly, such a colloidal templating method provides a superior flexibility and versatility in the material choice and architecture design of the final replica porous structure.This talk highlights the recent developments in our group in utilising binary colloidal templates for fabricating hierarchical materials and further functionalisations. We report a facile method in creating large area (cm scale) binary colloidal crystals via horizontal deposition within a couple of hours2. Their inverse replicas have been fabricated to expose the internal structures. The significant advantages of such a fabrication method lie in its simplicity, which requires no elaborated equipment, the fast production rate (about 2 hours over an area of 2.2x2.2 cm2), and the ability in handling large colloids (>600 nm). We will also present the unveiled formation mechanism in the presentation.