Fe-TiB₂ metal matrix composite, also called high-modulus steels (HMSs), are of great interest for applications in fuel-efficient transportation infrastructure, aerospace, and wear industries due to their high specific stiffness and yield strength. However, conventional cast Fe-TiB₂ HMSs often contain coarse and sharp-edged TiB₂ particles which easily trigger premature cracking during loading. Here, we synthesized a Fe-TiB₂ nanocomposite HMS via laser powder bed fusion (LPBF) additive manufacturing of mixed micro-sized powders of Fe, Ti, and Fe₂B. We investigated the microstructure formation and mechanical behavior of the Fe-TiB₂ HMS. We found that in situ chemical reaction of Ti and Fe₂B enables the formation of TiB₂ particles at nanoscale during rapid solidification of LPBF. These nanoscale TiB₂ particles can serve as heterogeneous nucleation sites and promote the formation of ultrafine and equiaxed α-Fe grains with random crystallographic textures, which differ from many other additively manufactured (AM) metal alloys characteristic of strong crystallographic textures. As such, isotropic mechanical properties were achieved in the AM Fe-TiB₂ nanocomposite HMS with a high elastic modulus of ∼ 240 GPa, an exceptional yield strength of ∼ 1450 MPa, and a large plasticity of ∼ 20% under compression. Quantitative analysis reveals that the high yield strength primarily originates from strengthening contributions of the ultrafine grains with an average grain size of ∼450 nm, the nanoscale TiB₂ reinforcing particles of 20–180 nm, and a high density of printing-induced dislocations of the order of 10¹⁵ m⁻². In situ synchrotron high-energy X-ray diffraction unveils the load partitioning from the softer α-Fe matrix to the stiffer and stronger TiB₂ nanoparticles, contributing to the sustained strain hardening during compression. Our work not only provides a general pathway for achieving high-performance metal matrix nanocomposites by in situ chemical reaction and precipitation of ceramic nanoparticles during additive manufacturing, but also offers mechanistic insights into the deformation mechanism of nanoparticle-reinforced HMS composites.