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A novel V–Nb–Mo steel was thermomechanically processed to promote ferrite grain refinement and precipitation during the austenite to ferrite transformation. Transmission electron microscopy and three-dimensional atom probe tomography confirmed the formation of two main types of precipitates: nano-scale interphase precipitates and fibrous precipitates (FP). Both the precipitates had a Baker–Nutting orientation relationship with the ferrite matrix, but with different variants. Interphase precipitates exhibited a disc shape with an average distance between precipitate rows of 15 ± 2 nm and an average Guinier radius of 3.9 ± 1.7 nm, whereas FP had a rod-shape 2.5 ± 0.5 nm in radius and 8–25 nm in length. It appeared that the FP are formed along the plane perpendicular to the interphase precipitates plane.