The precipitation behavior of M23C6 carbides in LF25 high nitrogen austenitic heat-resistant steel was investigated from 700 °C to 850 °C. The results demonstrated that the precipitates in LF25 steel included Nb (C, N) and M23C6 during the aging treatment. M23C6 carbides with four morphologies formed during aging followed a sequence of intergranular precipitates, parallel plate-like precipitates, cellular precipitates, and intragranular precipitates with increasing aging temperature. The four types of morphologies of M23C6 retained a cube-on-cube crystallographic relation with the matrix. Firstly, the M23C6 precipitated as discontinuous particles along the grain boundaries due to the faster diffusion rate of the elements. With the aging temperature increasing, intergranular M23C6 grew and connected to form a film-like morphology. The partial dislocations slipped out from the non-coherent twin boundaries due to the stresses resulting from quenching and elastic modulus together with atomic volume difference between the M23C6 and austenite matrix. M23C6 nucleated at the slipped dislocations and grew along the (111) or (110) planes to form a parallel plate-like morphology. Cellular precipitates were precipitated from supersaturated austenite matrix and then formed an alternating morphology of lamellae M23C6 and austenite during the discontinuous precipitation reaction. Due to high resistance to intracrystalline growth, the intragranular precipitates were short rods or granules with small sizes.