In this study, we investigated the precipitation behavior of the R-phase precipitated at the initial stage of aging and its effect on the pitting corrosion of 25%Cr-7%Ni-4%Mo super duplex stainless steel. The R-phase in super duplex stainless steel was mainly precipitated at the interface of ferrite/austenite phases and inside of the ferrite phase during the initial stage of aging, and it was transformed into the σ-phase with an increase in aging time. The ferrite phase was decomposed into a new austenite phase and σ-phase. The R phase was an intermetallic compound, which represented a lower Ni and higher Mo than the matrix, and also had a higher Mo and Cr concentration than the σ phase. With an increasing aging time, the pitting potential Ep was increased slowly by the precipitation of the R-phase, and it was then steeply decreased by the precipitation of the σ-phase. The R-phase was decreased the pitting potential, but its effect was smaller than effect of σ-phase.