Abstract: Deep-sea hydrothermal vent polymetallic sulfide deposits are enriched with high-value metals such as Cu, Zn, Ag, and Au, as well as rare and dispersed elements. However, the extreme deep-sea environment and complex mineral assemblages pose significant technical challenges across the entire "sampling-dissociation-extraction" chain. This study systematically reviews the research progress and technical bottlenecks in this field: Regarding sampling technology, the evolution from mechanical sampling to intelligent integrated systems is analyzed, identifying mineral phase transitions and oxidation issues caused by low sample fidelity. Solutions involving multi-parameter intelligent sensing and adaptive sampling systems are proposed. Concerning dissociation mechanisms, the oxidative dissolution kinetics of major minerals including pyrite, chalcopyrite, and sphalerite under pressure-temperature coupling conditions are elucidated. The galvanic effects, synergistic interactions, and competitive mechanisms in multi-mineral systems are revealed, emphasizing the need to establish cross-scale dissociation theoretical frameworks and kinetics databases. For green extraction technologies, the advantages and limitations of biometallurgy, electrochemical extraction, supercritical fluid extraction, and microwave-assisted extraction are summarized, with proposals for developing multi-technology synergistic integrated processes. Four breakthrough directions for future development are proposed: developing intelligent in-situ fidelity sampling equipment, deepening research on pressure-temperature coupling dissociation mechanisms, constructing integrated green extraction process systems, and establishing digital twin and intelligent collaborative control platforms for the entire sampling-dissociation-extraction process. The research outcomes provide theoretical guidance and technical support for the development of deep-sea mineral resources, holding significant importance for ensuring national resource security and advancing maritime power construction.