An anomalous increase in magnetization was investigated in a cold-rolled high-Mn TRIP steel (16.8 wt% Mn) annealed at 350°C for times varying from 5 to 120 min, before the start of austenite reversion (α’ → γ). Besides in-situ and ex-situ magnetic measurements, the full characterization of this phenomenon was also performed with the aid of X-ray diffraction (XRD), Mössbauer spectroscopy, and microstructural characterization using electron backscatter diffraction (EBSD) and atom probe tomography (APT). Based on XRD measurements, the volume fraction of austenite and α’-martensite was estimated as a function of annealing time, as well as their lattice strain. Phase quantification confirmed the absence of newly-fresh α’-martensite in the material during annealing at 350°C. Short annealing up to 15 min promoted the increase of Ms (saturation magnetization) due to stress relief in α’-martensite (Villari effect). Further annealing to 30 min promotes the decrease in Ms driven by short-range solute reorganization within the lattice. After 60 min annealing, the creation of long-range solute-depleted zones (i.e. confined zones highly enriched in Fe) causes a new increase in Ms. In comparison, for 120 min of annealing time, Ms tends to remain unaltered. These findings revealed that short- and long-range chemical fluctuations strongly affect the saturation magnetization of the steel and brought new insights on the use of magnetic probing as a tool for phase quantification in Mn-bearing steels.