Abstract: Seafloor massive sulphides(SMS)are high-grade hydrothermal deposits rich in copper, zinc and lead with a high gold and silver content, arousing great interest of international mining industry. In recent years, some international large-scale resource developers and investors such as Australia-based Nautilus Minerals Inc. that is a world leader in underwater mineral exploration have been involved in the commercial exploitation of SMS deposits. The present study introduces Nautilus's series of exploration and sampling programs which have been carried out in the Exclusive Economic Zone of Papua New Guinea for SMS deposits with the purpose of commercial exploitation, and simultaneously the methods and techniques for exploration and sampling, especially the equipments, results and efficiencies of dredge sampling, ROV grab sampling, drilling vessel core sampling and specialized ROV drill core sampling are introduced systematically and comprehensively.