Highly ordered bimodal mesoporous phosphosilicate monoliths were synthesized in a facile one-step sol-gel route, whose mesostructures were tuned via optimizing the addition time of trimethxyl phosphate. After the removal of surfactant, the bulk monoliths are glassy and present vitreous luster and fibrous patterns. The monoliths have a dual mesoporosity, consisting of two kinds of 20 hexagonal mesostructures with narrow pore size distributions. Their mesopores are partially connected together to form 3D pore networks and joints. These were examined and confirmed by small-angle X-ray diffraction, N-2 sorption, and transmission electron microscopy. The monoliths may find applications in catalysis, separation, and electrochemical devices.