Depth profiling investigation plays an important role in studying the dynamic processes of the ocean. In this paper, a newly developed hyphenated underwater system based on multi-optical spectrometry is introduced and used to measure seawater spectra at different depths with the aid of a remotely operated vehicle (ROV). The hyphenated system consists of two independent compact deep-sea spectral instruments, a deep ocean compact autonomous Raman spectrometer and a compact underwater laser-induced breakdown spectroscopy system for sea applications (LIBSea). The former was used to take both Raman scattering and fluorescence of seawater, and the LIBS signal could be recorded with the LIBSea. The first sea trial of the developed system was taken place in the Bismarck Sea, Papua New Guinea, in June 2015. Over 4000 multi-optical spectra had been captured up to the diving depth about 1800 m at maximum. The depth profiles of some ocean parameters were extracted from the captured joint Raman–fluorescence and LIBS spectra with a depth resolution of 1 m. The concentrations of [Formula: see text] and the water temperatures were measured using Raman spectra. The fluorescence intensities from both colored dissolved organic matter (CDOM) and chlorophyll were found to be varied in the euphotic zone. With LIBS spectra, the depth profiles of metallic elements were also obtained. The normalized intensity of atomic line Ca(I) extracted from LIBS spectra raised around the depth of 1600 m, similar to the depth profile of CDOM. This phenomenon might be caused by the nonbuoyant hydrothermal plumes. It is worth mentioning that this is the first time Raman and LIBS spectroscopy have been applied simultaneously to the deep-sea in situ investigations.