The objective of this research is to determine the longitudinal stress in rails by using the polarization of Rayleigh waves. Analytical models are developed to describe the effect of applied stress on wave speed and on the polarization of Rayleigh waves. A numerical simulation is performed to find the effect of applied stress on wave velocity and Rayleigh wave polarization. The effect of uncertainties in material properties on wave velocity and polarization of Rayleigh wave is also examined in the simulation. The experiment uses a laser Doppler vibrometer (LDV) to measure the particle velocities. The in-plane and out-of-plane velocity components are obtained from the measured particle velocities. The polarization of Rayleigh wave, which is defined as the ratio between the in-plane and out-of-plane displacements, is calculated. Furthermore, the polarization of the Rayleigh wave is considered as a measure to identify applied stress. The experiment is performed on unstressed and stressed rail specimen. Thus, Rayleigh wave polarization is obtained as a function of applied stress. The experimental results are compared with the analytical model. The result shows a good agreement with the theoretical values for unstressed rail.