The cleanliness and functionalization of metal surfaces are critical factors to determining their performance in high-performance microelectronic packaging, reliable biomedical implants, advanced composite bonding, and other fields. Compared to traditional wet cleaning methods, plasma cleaning technology has emerged as a research hotspot in surface engineering due to its unique advantages, such as high efficiency and environmental friendliness. It operates under versatile conditions (e.g., power: tens of watts to several kilowatts; pressure: atmospheric to low vacuum; treatment time: seconds to minutes), enabling not only efficient contaminant removal but also targeted surface functionalization, including dramatically enhanced hydrophilicity (e.g., contact angles from >80° to <10°), significantly improved adhesion (e.g., up to 40% increase in bond strength), and modifications in surface roughness, corrosion resistance, and biocompatibility. This review systematically elaborates on the physical, chemical, and synergistic mechanisms of plasma cleaning technology as it acts on metal surfaces. It focuses on plasma cleaning applied to copper, aluminum, titanium and their respective alloys, as well as alloy steels, providing a detailed analysis of contaminant types, plasma cleaning methodologies, common challenges, surface functionalization responses, and subsequent functional applications. Furthermore, this review discusses the current challenges faced by plasma cleaning technology and offers perspectives on its future development directions. It aims to systematize the research progress in plasma cleaning of metal surfaces, thereby facilitating the transition of this technology towards large-scale industrial applications for metal surface functionalization.