Interfaces between a liquid and a solid (L-S) are the most important surface science in chemistry, catalysis, energy, and even biology. Formation of an electric double layer (EDL) at the L-S interface has been attributed due to the adsorption of a layer of ions at the solid surface, which causes the ions in the liquid to redistribute. Although the existence of a layer of charges on a solid surface is always assumed, the origin of the charges is not extensively explored. Recent studies of contact electrification (CE) between a liquid and a solid suggest that electron transfer plays a dominant role at the initial stage for forming the charge layer at the L-S interface. Here, we review the recent works about electron transfer in liquid-solid CE, including scenerios such as liquid-insulator, liquid-semiconductor, and liquid-metal. Formation of the EDL is revisited considering the existence of electron transfer at the L-S interface. Furthermore, the triboelectric nanogenerator (TENG) technique based on the liquid-solid CE is introduced, which can be used not only for harvesting mechanical energy from a liquid but also as a probe for probing the charge transfer at liquid-solid interfaces.