The　conversion　of　waste　cooking　oil　(WCO)　to　biodiesel　is　promising　in　the　green　energy　and　sustainable　development　sector.　In　this　study,　ionic　liquid@amphiphilic　silica　nanoparticles　(IASNPs)　combining　the　aspects　of　amphiphilic　Pickering　emulsions　and　acidic　ionic　liquids　(ILs)　were　developed　for　green　biodiesel　production　from　the　transesterification　of　WCO　and　methanol.　Based　on　the　interesting　principle　of　interfacial　catalysis　in　a　Pickering　emulsion,　this　novel　catalyst　could　effectively　promote　the　catalytic　reaction　occurring　at　the　three-phase　interface　by　constructing　water-in-oil　microdroplets　(with　each　microdroplet　being　considered　a　microreactor)　without　any　surfactant　additives,　considerably　overcoming　the　disadvantage　of　limited　mass-transfer　ability　in　heterogeneous　catalysis.　This　synergistic　effect　between　the　amphiphilic　nature　and　IL　acidic　catalysis　was　well　optimized　during　the　construction　of　IASNPs,　and　the　Box-Behnken　response　surface　methodology　was　used　to　optimize　the　operating　conditions　of　biodiesel　production.　The　results　showed　that　an　ultrahigh　biodiesel　yield　of　91.45%　was　obtained　under　optimum　conditions,　even　without　mechanical　stirring.　Furthermore,　there　was　little　loss　of　biodiesel　yield　after　six　cycles　via　simple　centrifugation,　validating　its　ease　of　recovery,　robust　catalytic　stability,　and　low　cost.　Our　work　provides　an　important　methodology　and　catalyst　design　tool　for　the　green　and　sustainable　reutilization　of　WCO.