Polyelectrolyte-surfactant complexes (PESCs) have long been employed as oil-in-water (o/w) emulsions stabilizers, but never in the structure of colloidal complex coacervates providing a Pickering effect. The complexed state of PESCs could make them unsuitable o/w Pickering emulsifiers, which instead require a balance between colloidal structure and stability, amphiphilicity and wettability. Here we hypothesize that PESCs coacervates are efficient Pickering stabilizers. Instead of classical surfactants, we employ sophorolipid (SL) biosurfactants, atypical anionic/neutral stimuli-responsive biosurfactants. Despite their tunable charge and mild amphiphilic character, they can be used in combination with cationic/neutral polyelectrolytes (chitosan, CHL, or poly-L-lysine, PLL) to form PESC coacervates for the development of biobased, but also pH-switchable, Pickering emulsions. Aqueous solutions of SL-CHL (or SL-PLL) complex coacervates are emulsified with dodecane. Confocal laser scanning microscopy (CLSM) and scanning electron microscopy under cryogenic conditions (cryo-SEM) demonstrate the Pickering effect, while optical microscopy and oscillatory rheology respectively assess the emulsion formation and relative viscoelastic properties. Both SL-CHL and SL-PLL PESCs stabilize o/w emulsions up to Φoil of 0.7 only in the pH region of complex coacervation (6 < pH < 9): outside this range, phase separation occurs. Rheology shows a typical solid-like response and mechanical recovery upon applying large deformations. CLSM and cryo-SEM highlight a colloidal structure, associated to the complex coacervates, of the oil/water interface and suggest a Pickering effect. These findings demonstrate the Pickering effect from PESC coacervates and the possibility to use biobased and biocompatible components, with application potential in cosmetics, food science, or oil recovery.