The particle size of submicron particles significantly affects their properties; thus, the accurate measurement of submicron particle size is essential to ensure its excellent properties. Polarized light scattering is an important tool for measuring the particle size of the ensemble of particles in suspension. However, in the existing measurement systems, the polarized scattered light is detected using a CCD detector or an array of single-point detectors. The CCD detector misses a large part of the polarized scattered light due to its narrow detection range of scattering angles, and the array of single-point detectors has the problem of low angular resolution due to the limited number of detectors. According to the above problems, this paper designs a submicron particle size measurement method based on the polarization difference in polarized scattered light with high angular resolution. The vertically and horizontally polarized scattered light was acquired with high angular resolution (angular separation = 2°) over a scattering angle range of 50°–110° using a photomultiplier coupled with a turntable. The scattering angle of the acquired vertically and horizontally polarized scattered light were corrected to eliminate the scattering angle deviations caused by obliquely incident light, and then the polarization difference in the vertically and horizontally polarized scattered light was computed, from which the submicron particle size distribution was inverted subsequently. Experiments were performed using polystyrene microsphere standard particles with particle sizes of 350 nm, 200 nm, and 100 nm. The experimental results show that (1) the Pearson correlation coefficient of the linearly fitted curve of the corrected polarization difference to the theoretical polarization difference is larger than 0.997, and the slope and intercept of the linearly fitted curve are, respectively, close to 1 and 0, indicating that the corrected polarization difference is highly consistent with the theoretical polarization difference; (2) the mean relative error and coefficient of variation of the particle size distribution parameter D50 obtained from the polarization difference with high angular resolution (angular separation = 2°) are better than those of the parameter D50 obtained from the polarization difference with low angular resolution (angular separation = 12°), indicating better accuracy and repeatability of the particle size distribution inverted from the polarization difference with high angular resolution; and (3) for the particle size distribution parameters D10, D50, and D90 obtained from the scattering angle-corrected polarization difference with high angular resolution, the deviation of the measured values from the average value are all smaller than the thresholds given in the international standard, indicating a good repeatability of the proposed method.