Carbon-fiber-reinforced polymer (CFRP) is a type of composite material with many superior performances, such as high tensile strength, light weight, corrosion resistance, good fatigue, and creep performance. As a result, CFRP cables have great potential to replace steel cables in prestressed concrete structures. However, the technology to monitor the stress state in real-time throughout the entire life cycle is very important in the application of CFRP cables. Therefore, an optical–electrical co-sensing CFRP cable (OECSCFRP cable) was designed and manufactured in this paper. Firstly, a brief description is outlined for the production technology of the CFRP-DOFS bar, CFRP-CCFPI bar, and CFRP cable anchorage technology. Subsequently, the sensing and mechanical properties of the OECS-CFRP cable were characterized by serious experiments. Finally, the OECS-CFRP cable was used for the prestress monitoring of an unbonded prestressed RC beam to verify the feasibility of the actual structure. The results show that the main static performance indexes of DOFS and CCFPI meet the requirements of civil engineering. In the loading test of the prestressed beam, the OECS-CFRP cable can effectively monitor the cable force and the midspan defection of the beam so as to obtain the stiffness degradation of the prestressed beam under different loads.