Contact electrification (CE) is a common physical process by which triboelectric charges are generated through the mutual contact between two objects. Despite the ongoing debates on CE’s mechanism, recent advancements in technology have elucidated the primary role of electron transfer in most CE processes. This discovery leads to the spawning of an emerging field, known as contact-electro-catalysis (CEC), which utilizes the electron transfer phenomenon during CE to initiate CEC. In this work, we provide the first comprehensive review of the recent progress of the solid–liquid interface-mediated CEC process, including its working principles, relationship with surface science, recent breakthroughs in applications, and future challenges. We aim to provide fundamental guidance for researchers to understand the reaction mechanism of the CEC process and to propose potential pathways to enhance CEC efficiency from a surface and interfacial science perspective. Later, recent application scenarios using the novel CEC techniques are summarized, including wastewater treatment, efficient generation of hydrogen peroxide (H2O2), lithium-ion battery recycling, and CO2 reduction. In general, CEC technology has opened a new avenue for catalysis, effectively expanding the range of catalyst options and holding promise as a solution to a variety of complex catalytic challenges in the future.