Biological amphiphiles are molecules with a rich phase behavior. Micellar, vesicular, and even fibrillar phases can be found for the same molecule by applying a change in pH or by selecting the appropriate metal ion. The rich phase behavior paves the way toward a broad class of soft materials, from carriers to hydrogels. The present work contributes to understanding the fibrillation of a microbial glycolipid, glucolipid G-C18:1, produced by Starmerella bombicola ΔugtB1 and characterized by a micellar phase at alkaline pH and a vesicular phase at acidic pH. Fibrillation and prompt hydrogelation is triggered by adding either alkaline earth, Ca2+, or transition metal, Ag+, Fe2+, Al3+, ions to a G-C18:1 micellar solution. A specifically designed apparatus coupled to a synchrotron SAXS beamline allows the performing of simultaneous cation- and pH-resolved in situ monitoring of the morphological evolution from spheroidal micelles to crystalline fibers, when Ca2+ is employed, or to wormlike aggregates, when Fe2+ or Al3+ solutions are employed. The fast reactivity of Ag+ and the crystallinity of Ca2+-induced fibers suggest that fibrillation is driven by direct metal-ligand interactions, while the shape transition from spheroidal to elongated micelles with Fe2+ or Al3+ rather suggest charge screening between the lipid and the hydroxylated cation species.