Hierarchically structured porous materials are of great interest to catalysis, where an accurately controlled pore texture at different length scales can help to reduce or otherwise control transport limitations. A method is presented to synthesize bimodal structured silicas, with an independently controlled small meso- and large meso-to macroporosity. Small primary MCM-41 particles assemble around micelles formed by a tri-block copolymer surfactant that is added as a low-concentration ethanolic solution to the particles, while these still form a flexible gel. Cross-linking of the particles in an autoclave, followed by drying and calcination, leads to bimodal materials with the controlled small mesopores of MCM-41, and a larger meso- to macropore size distribution that depends on the micelle shape and size. The latter is a function of the conditions in the second step, such as the amount and composition of the surfactant, the aging time, the temperature, the pH and the type of solvent. Fine tuning of this procedure, application to other primary structured particles, and combination with other structuring methods, should enable to construct multi-structured hierarchical materials with a desired texture at all scales.