Stimuli-responsive glycolipid biosurfactants belonging to the family of acidic sophorolipids (SL) have been used to introduce a broad range of pore size in the mesoscale regime (2–30 nm) in silica particles using a one-pot co-assembly sol–gel route in water. The pore size distribution is tailored by the sole interaction between an amino-modified silane, aminopropyltriethoxy silane (APTES), and SL. No additional compounds (e.g., block copolymers, polymers, organic solvents, pore-swelling agents) have been used to promote the formation of mesopores larger than 2 nm. Materials morphology and porosity have been characterized by high resolution TEM, SEM, and nitrogen physisorption, while the interaction between the glycolipid and silica is demonstrated by FT-IR and solid-state NMR.