Spectroscopic sensor is becoming an important issue for the deep-sea exploration due to the advantages of multi-specie, multi-phases and stand-off detection. Different approach have been developing in recent years based on LIBS (Laser Induced Breakdown Spectroscopy) and Raman spectroscopy since Raman-LIBS are complementary techniques with the similar components and the capability of molecular and elementary analysis. In this work, we built a LIBS-Raman system and detected Na2SO4 in aqueous solution to evaluate the potential ocean application. With the same laser, spectrometer and detector, a hybrid of Raman and LIBS system was developed to realize the detection of anions and cations in the seawater. The optics was composed by two parts. Raman channel and LIBS channel, and the signal was collected by a Y type optical fiber bundle. The signal from two channels was separated by imaging on different arrays of the CCD detector. The Raman spectra of SO4(2-) and LIBS spectra of Na was successfully detected simultaneously when the pulse energy was above 3.6 mJ. However, due to the strong bremsstrahlung radiation of LIBS, the signal to noise ratio of Raman was significantly decreased as the laser energy increasing. The results manifested the great potential of Raman-LIBS combination for the underwater detection.