Discontinuous precipitation (DP) reactions is a grain boundary (GB) diffusion-controlled phenomenon generating lamellar or rod-type equilibrium precipitates driven by a migrating GB that acts as a fast reaction path under the action of chemical and capillary forces, leaving behind a regularly spaced array of precipitates growing cooperatively from the supersaturated matrix. In multicomponent alloy systems containing both substitutional and interstitial solutes, DP usually is constituted of either Cr-rich M23C6 or Cr2N lamellae [1,2]. Recently, σ-phase has been observed as the main precipitate comprising a DP colony in superaustenitic stainless steel [3]. The DP reactions are of practical interest because of its effect on corrosion and mechanical properties of alloys under service conditions [1,2]. The present investigation deals with the DP reaction in Alloy 33 with an austenitic matrix and nominal composition (wt. %) 33Cr-32Fe-31Ni-1.6Mo-0.6Cu-0.4N. In order to understand the DP behavior upon isothermally aging at 800°C, an experimental study has been conducted using scanning electron microscopy (SEM), scanning and transmission electron microscopy (STEM/TEM) with X-ray energy dispersive spectroscopy (XEDS), and electron backscatter diffraction (EBSD). Detailed microstructural analysis was performed using an FEI Talos F200A with Super X (4 Si Drift Detectors) and X-FEG for high sensitivity STEM-EDX spectrum imaging and analysis on electron-transparent thin-foil specimens prepared by the twin-jet electropolishing technique.