The connection between the austenite transformation and pitting corrosion of lean duplex stainless steel LDX 2101 was investigated at different annealing temperatures in the range 950–1200 °C. Optical microscopy, scanning electron microscopy, and electrochemical techniques were employed in the present work. Results indicated that micro-sized ferrite and austenite grains, formed with the increase of annealing temperature, influenced the pitting corrosion resistance of the studied stainless steel. As the austenite phase transformed into ferrite, the micro-sized ferrite grains were produced in austenite domains with temperature increase from 1000 °C to 1100 °C, especially at 1050 °C. In these conditions, the corrosion resistance of LDX 2101 was reduced by the micro-sized ferrite grains. A further increase of annealing temperature to 1150 °C produced the presence of micro-sized austenite grains in the ferritic phase, due to an incomplete transformation of austenite to ferrite. They represent new sites for severe pitting attacks and therefore the corrosion resistance of LDX 2101 was the weakest. The sample annealed at 1200 °C, with few micro-sized austenite grains in the ferritic matrix, exhibited excellent corrosion resistance. Moreover, a schematic was used to illustrate the pitting corrosion of the samples annealed at different temperatures.