This study investigates the mechanism of liquid-solid contact electrification (CE) on superhydrophobic surfaces, revealing that electron transfer, rather than ion transfer, is the primary cause of charge generation. By designing binary superhydrophobic surfaces with tunable work functions, the researchers decouple electron and ion transfer processes. These surfaces, composed of mercaptan molecules with opposite electron-donating/accepting properties, allow precise control over surface properties, enabling regulation of charge polarity and magnitude during CE. The study demonstrates a linear relationship between the work function of superhydrophobic surfaces and the generated charges in liquids, indicating that CE arises from electron transfer driven by the work function difference between the liquid and solid surfaces. The researchers also rule out ion transfer on superhydrophobic surfaces by proving the absence of ions after contact with ion-enriched liquids. This finding contrasts with previous studies and offers new insights into the mechanisms of CE, potentially enabling broader applications. The study shows that superhydrophobic surfaces can either positively or negatively electrify liquids, independent of pH and ion types, due to their strong liquid-repelling properties. The results highlight the importance of surface properties in controlling CE and provide a framework for further exploration of practical applications in areas such as microfluidics and interfacial chemistry.This study investigates the mechanism of liquid-solid contact electrification (CE) on superhydrophobic surfaces, revealing that electron transfer, rather than ion transfer, is the primary cause of charge generation. By designing binary superhydrophobic surfaces with tunable work functions, the researchers decouple electron and ion transfer processes. These surfaces, composed of mercaptan molecules with opposite electron-donating/accepting properties, allow precise control over surface properties, enabling regulation of charge polarity and magnitude during CE. The study demonstrates a linear relationship between the work function of superhydrophobic surfaces and the generated charges in liquids, indicating that CE arises from electron transfer driven by the work function difference between the liquid and solid surfaces. The researchers also rule out ion transfer on superhydrophobic surfaces by proving the absence of ions after contact with ion-enriched liquids. This finding contrasts with previous studies and offers new insights into the mechanisms of CE, potentially enabling broader applications. The study shows that superhydrophobic surfaces can either positively or negatively electrify liquids, independent of pH and ion types, due to their strong liquid-repelling properties. The results highlight the importance of surface properties in controlling CE and provide a framework for further exploration of practical applications in areas such as microfluidics and interfacial chemistry.