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Abstract Understanding the evolution of massive binary stars requires accurate estimates of their masses. This understanding is critically important because massive star evolution can potentially lead to gravitational-wave sources such as binary black holes or neutron stars. For Wolf–Rayet (WR) stars with optically thick stellar winds, their masses can only be determined with accurate inclination angle estimates from binary systems which have spectroscopic M sin i measurements. Orbitally phased polarization signals can encode the inclination angle of binary systems, where the WR winds act as scattering regions. We investigated four Wolf–Rayet + O star binary systems, WR 42, WR 79, WR 127, and WR 153, with publicly available phased polarization data to estimate their masses. To avoid the biases present in analytic models of polarization while retaining computational expediency, we used a Monte Carlo radiative-transfer model accurately emulated by a neural network. We used the emulated model to investigate the posterior distribution of the parameters of our four systems. Our mass estimates calculated from the estimated inclination angles put strong constraints on existing mass estimates for three of the systems, and disagree with the existing mass estimates for WR 153. We recommend a concerted effort to obtain polarization observations that can be used to estimate the masses of WR binary systems and increase our understanding of their evolutionary paths.