The traditional azimuth transmission technology based on magneto-optical modulation requires linear propagation of a beam and has a limited application scope. To solve this problem, a non-line-of-sight azimuth transmission technology is proposed based on polarization-maintaining fiber. First, the compositions of the system are introduced and the working principle of the system is presented. Then, by analyzing the effect of birefringence effect of a polarization-maintaining fiber on the phase difference of the transmission vector, a polarization-maintaining fiber Jones matrix containing phase difference is constructed. Finally, the Jones matrix is used to transform the Maxwell columns of the light vector, the azimuth solving model is derived, and the simulation analysis is carried out. The results show that the theoretical error of misaligned azimuth can be controlled within 0.1″ when the phase difference is not equal to π/2. In contrast, when the phase difference is π/2, the azimuth is always 0, and the error increases proportionally with the azimuth. The conclusion shows that the feasibility of this technique in azimuth transmission is confirmed. The proposed method extends the azimuth transmission mode and is of great significance to both the improvement of the non-line-of-sight azimuth transmission technology based on polarization-maintaining fiber and the improvement of the measurement accuracy of the system.