The accurate location of optical fiber composite overhead ground wire (OPGW) connection towers and fiber breakpoints is of great significance to the operation and maintenance of power communication networks. At present, during OPGW fault location, the optical time-domain reflectometer (OTDR) is generally used to measure breakpoint distances and attenuation information. Since the OTDR measurement result is fiber length, which does not correspond to the physical distance recorded in the tower schedule. In addition, the OTDR is limited by the spatial resolution when measuring long distances, making the fiber connection points and fiber breakpoints do not correspond to the towers. In response, this paper proposed a method that used the Brillouin frequency shift hopping in multiple fiber cores and the characteristics of the Brillouin frequency shifts of the downleads to achieve precise location of the OPGW connection towers. Precise OPGW fault location was achieved by comparing the Brillouin frequency shifts of the broken fiber cores and the intact fiber core. Moreover, the method proposed in this paper has been initially applied in actual OPGW line operation and maintenance. As a result, precise location of the OPGW connection towers and the faulty fiber cores have been achieved. This study provides a new technical support method for the refined operation and maintenance of the OPGW.