With their unique capability to deal with a considerable geographic area, satellite–ground–underwater optical wireless communication (OWC) systems are an appealing alternative to meet the ever-increasing demand for end-to-end broadband services. Using four different Laguerre–Gaussian (LG) modes, an orbital angular momentum (OAM) multiplexing method was developed to enhance the spectral efficiency and system capacity of the satellite–ground–underwater OWC system. At an aggregate throughput of 160 Gbps, LG[0,0], LG[0,2], LG[0,4], and LG[0,8] were realized. Various atmospheric conditions, water types, and scintillation effects were used to evaluate the performance of two separate OWC links for satellite-to-ground and ground-to-underwater communication. A maximum OWC range of 21,500–30,000 km has been obtained under weak-to-strong turbulence for satellite-to-ground scenarios, and a range of 12–27 m underwater for ground-to-underwater scenarios under various scintillation effects. At LG[0,0], in pure sea, the maximum gain is −75.02 dB, the noise figure is 75.02 dB, the output signal is −78.32 dBm, and the signal-to-noise ratio is 21.67 dB. In comparison with other works in the literature, this system shows a superior performance.