The exploitation and research of deep-sea hydrothermal vent has been an issue of great interest in ocean research in recent years. Laser-induced breakdown spectroscopy (LIBS) has great potential for ocean application due to the capabilities of stand-off, multiphase, and multielement analysis. In this work, a newly developed compact 4000 m rated LIBS system (LIBSea) is introduced with preliminary results of sea trials. The underwater system consists of an Nd:YAG single-pulsed laser operating at 1064 nm, an optical fiber spectrometer, an optics module, and an electronic controller module. The whole system is housed in an L800 mm×ϕ258 mm pressure housing with an optical window on the end cap. It was deployed on the remote operated vehicle Faxian on the research vessel Kexue, and in June 2015 was successfully applied for hydrothermal field measurements at the Manus area. The obtained results are shown that the LIBS system is capable of detecting elements Li, Na, K, Ca, and Mg in the hydrothermal area. Profiles of LIBS signals of elements K and Ca have also been obtained during the sea trial. The results show that the K emission line is gradually broadened with depth from sea surface to sea floor (1800 m or so); the K intensity shows a hump shape with maximum value at about 1050 m. The Ca emission line is rapidly broadened below 400 m and slowly narrowed to the sea floor; the Ca intensity shows no obvious change below 400 m and increases continuously to sea floor. A very interesting finding is that the small fluctuations of intensity profile curve of Ca show a degree of correlation with seawater temperature change. The sea trial results prove the performance of LIBSea. After further optimization, it is hoped to apply the LIBS system to the in situ mineral deposits and hydrothermal vent fluid detection in deep sea.