This study investigates the contact electrification (CE) between liquids and superhydrophobic surfaces, focusing on the role of electron transfer. By designing binary superhydrophobic surfaces using self-assembled monolayers of mercaptan molecules with opposite electron-donating/accepting properties (1H,1H,2H,2H-perfluorodecanethiol [FDT] and n-decanethiol [DT]), the researchers achieve a decoupling of electron and ion carriers during CE. The work function of these surfaces can be modulated by adjusting the molar ratio of FDT and DT, allowing control over the polarity and magnitude of static charges generated in liquids. The results show a linear relationship between the work function of the surfaces and the generated charges, indicating that electron transfer is driven by the work function difference. The study also demonstrates that superhydrophobic surfaces can generate both positive and negative charges in liquids, regardless of the pH levels of the liquids, which contrasts with existing findings where liquid-solid CE is pH-dependent. Additionally, the surfaces effectively prevent ion transfer, as evidenced by the stable surface potential and charging ability after contact with ion-enriched liquids. These findings provide new insights into liquid-solid CE and open up potential applications in various fields.This study investigates the contact electrification (CE) between liquids and superhydrophobic surfaces, focusing on the role of electron transfer. By designing binary superhydrophobic surfaces using self-assembled monolayers of mercaptan molecules with opposite electron-donating/accepting properties (1H,1H,2H,2H-perfluorodecanethiol [FDT] and n-decanethiol [DT]), the researchers achieve a decoupling of electron and ion carriers during CE. The work function of these surfaces can be modulated by adjusting the molar ratio of FDT and DT, allowing control over the polarity and magnitude of static charges generated in liquids. The results show a linear relationship between the work function of the surfaces and the generated charges, indicating that electron transfer is driven by the work function difference. The study also demonstrates that superhydrophobic surfaces can generate both positive and negative charges in liquids, regardless of the pH levels of the liquids, which contrasts with existing findings where liquid-solid CE is pH-dependent. Additionally, the surfaces effectively prevent ion transfer, as evidenced by the stable surface potential and charging ability after contact with ion-enriched liquids. These findings provide new insights into liquid-solid CE and open up potential applications in various fields.