Superaustenitic stainless steels (SSS) are widely used in extreme environments such as off-shore oil wells, chemical and food processing equipment, and seawater systems due to their excellent corrosion resistance and superior toughness. The design of the corresponding heat treatment process is crucial to create better mechanical properties. In this respect, the short-term annealing behavior of CN3MN grade SSS was investigated by a combined study of Charpy impact tests, hardness measurements, scanning and transmission electron microscopy. Specimens were heat treated at 1200 K (927 °C) for up to 16 minutes annealing time and their impact strengths and hardnesses were tested. The impact toughness was found to decrease to less than the half of the initial values while hardness stayed the same. Detailed fracture surface analyses revealed a ductile to brittle failure transition for relatively short annealing times. Brittle fracture occurred in both intergranular and transgranular modes. SEM and TEM indicated precipitation of nano-sized intermetallics, accounting for the intergranular embrittlement, along the grain boundaries with respect to annealing time. The transgranular fracture originated from linear defects seen to exist within the grains. Close observation of such defects revealed stacking-fault type imperfections, which lead to step-like cracking observed in microlength scales.