In this paper, we studied an original synthetic strategy to prepare bio-based surfactants by direct solvent-free etherification of glycerol with dodecanol using heterogeneous interfacial acidic catalysts dubbed Pickering Interfacial Catalysis. The conversion of dodecanol could be achieved to 60–71% with limited production of didodecyl ether (DE) as the main side product. The selectivity of the final product, alkylpolyglycerylether (AGEM), could be pushed to >80% with a water removal process at 150 °C, as a mixture of monolauryl polyglyceryl ethers, multilauryl polyglyceryl ethers and multilauryl cyclicpolyglyceryl ethers. AGEM could be isolated with a suitable work-up and was fully characterized by GC (MS), HPLC, SFC/HRMS, etc. The physicochemical properties of these new surfactants were evaluated, as well as their laundry performances. This solvent-free direct etherification process paves the way towards new value-added applications of glycerol.