The blending of mesoporosity with the properties of semiconductors promises new types of multifunctional nanomaterials. It would be particularly interesting to combine the shape selectivity of a mesoporous oxide with the electronic and photonic characteristics of a useful semiconductor. We demonstrated the synthesis of a mesoporous germanium semiconductor using liquid-crystals-templated chemistry. The template removal was achieved by a two-step ion-exchange thermal procedure. This semiconductive mesoporous form of germanium possesses hexagonal pore ordering with very high surface area and exhibits strongly size-dependent optical properties as well as photoluminescence.