The detection of dissolved gases in seawater plays an important role in ocean observation and exploration. As a potential technique for oceanic applications, Raman spectroscopy has already proved its advantages in the simultaneous detection of multiple species during previous deep-sea explorations. Due to the low sensitivity of conventional Raman measurements, there have been many reports of Raman applications on direct seawater detection in high-concentration areas, but few on undersea dissolved gas detection. In this work, we have presented a highly sensitive Raman spectroscopy (HSRS) system with a special designed gas chamber for small amounts of underwater gas extraction. Systematic experiments have been carried out for system evaluation, and the results have shown that the Raman signals obtained by the innovation of a near-concentric cavity was about 21 times stronger than those of conventional side-scattering Raman measurements. Based on this system, we have achieved a low limit of detection of 2.32 and 0.44 μmol/L for CO2 and CH4, respectively, in the lab. A test-out experiment has also been accomplished with a gas-liquid separator coupled to the Raman system, and signals of O2 and CO2 were detected after 1 h of degasification. This system may show potential for gas detection in water, and further work would be done for the improvement of in situ detection.