The aim of this study is to investigate the precipitation of intermetallic phases, especially the chi-phase, in a 45N (type UNS S31803) duplex stainless steel through aging heat-treatments carried out at 700 and 750 °C. Two intermetallic phases are detected: chi (χ) and sigma (σ). The χ-phase precipitates at ferrite/ferrite grain boundaries prior to the σ-phase precipitation, which occurs preferentially at ferrite/austenite interfaces and at ferrite/ferrite grain boundaries. The σ-phase precipitation is a eutectoid type reaction of ferrite leading to σ-phase phase and austenite. The χ-phase is consumed in the σ-phase precipitation after becoming completely surrounded by both the σ-phase and the newly formed austenite.