Hydrogels have emerged as effective evaporator platforms, significantly enhancing evaporation rates by disrupting water's hydrogen bond network. Here, we present an advanced strategy to improve hydrogel evaporation performance by tailoring alkyl hydrophobic groups within biparental polyelectrolyte-shell micelles grafted onto the polyvinyl alcohol (PVA) hydrogel surface. Poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA) quaternized with methyl iodide (MeI) or ethyl iodide (EtI) formed the biparental polyelectrolyte shell, while poly(benzyl methacrylate) (PBzMA) constituted the micelle core, creating BE-MeI and BE-EtI micelles, respectively. The molecularly engineered BE-MeI micelles exhibited an optimized configuration of quaternary amines linked to hydrophobic groups, achieving a synergistic balance between water attraction