The cathodoluminescence (CL) spectrum arising from diamagnetic point defects of silicon oxynitride lattice was analyzed to extract quantitative information on local stress fields stored on the surface of a silicon nitride polycrystal. A calibration procedure was preliminarily made to obtain a relationship between CL spectral shift and applied stress, according to the piezo-spectroscopic effect. In this calibration procedure, we used the uniaxial stress field developed in a rectangular bar loaded in a four-point flexural jig. Stress dependence was clearly detected for the most intense spectral band of a doublet arising from diamagnetic (Si-Si) defects, which was located at around 340 nm. The shallow nature of the electron probe enabled the characterization of surface stress fields with sub-micrometer-order spatial resolution. As applications of the PS technique, the CL emission from Si-Si defects was used as a stress probe for visualizing the residual stress fields stored at grain-boundary regions and at the tip of a surface crack propagated in polycrystalline silicon nitride.