In this contribution, we report about the synthesis, the aggregation properties and their application in cross-coupling catalysis of two new designer surfactants comprising a rigid hydrophobic portion based on β-sitosterol directly linked by an etheric bond to methyl polyoxoethylene chains. The proposed amphiphilic compounds represent a minimalistic approach with respect to the Lipshutz's third generation designer surfactant Nok. The amphiphiles displayed improved chemical stability, shorter synthesis, and good properties in Pd-catalyzed cross-coupling reactions in water under mild conditions, as compared with other neutral commercially available surfactants.