Chemical mechanical polishing (CMP) is an essential technology used in the semiconductor industry to polish and planarize a variety of materials for the fabrication of microelectronic devices (e.g., computer chips). During the high shear (~1,000,000 s(-1)) CMP process, it is hypothesized that individual slurry particles are driven together to form large agglomerates (≥0.5 μm), triggering a shear thickening effect. These shear-induced agglomerates are believed to cause defects during polishing. In this study, we examined the shear thickening of a 25 wt % fumed silica slurry with 0.17 M added KCl using in situ small-angle light scattering during rheological characterization (rheo-SALS). The salt-adjusted slurry displays a ~3-fold increase in viscosity at a critical shear rate of 20,000 s(-1) during a stepped shear rate ramp from 100 to 25,000 s(-1). As the shear rate is reduced back to 100 s(-1), the slurry displays irreversible thickening behavior with a final viscosity that is 100-times greater than the initial viscosity. Corresponding rheo-SALS images indicate the formation of micrometer scale structures (2-3 μm) that directly correlate with the discontinuous and irreversible shear thickening behavior of the fumed silica slurry; these micrometer scale structures are 10-times the nominal particle diameter (~0.2 μm). The scattering patterns from the 25 wt % slurry were corroborated through rheo-SALS examination of 27 and 29 wt % slurries (C(KCl) = 0.1 M). All slurries, regardless of ionic strength and solids loading, display scattering patterns that are directly associated with the observed thickening behavior. Scattering was only observable during and after thickening (i.e., no scattering was detected in the absence of thickening). This work serves as the first in situ observation of micrometer scale structures within the fumed silica CMP slurry while under shear.