AbstractTarget subsurface reservoirs for emerging low‐carbon energy technologies and geologic carbon sequestration typically have low permeability and thus rely heavily on fluid transport through natural and induced fracture networks. Sustainable development of these systems requires deeper understanding of how geochemically mediated deformation impacts fracture microstructure and permeability evolution, particularly with respect to geochemical reactions between pore fluids and the host rock. In this work, a series of triaxial direct shear experiments was designed to evaluate how fractures generated at subsurface conditions respond to penetration of reactive fluids with a focus on the role of mineral precipitation. Calcite‐rich shale cores were directly sheared under 3.5 MPa confining pressure using BaCl2‐rich solutions as a working fluid. Experiments were conducted within an X‐ray computed tomography (xCT) scanner to capture 4‐D evolution of fracture geometry and precipitate growth. Three shear tests evidenced nonuniform precipitation of barium carbonates (BaCO3) along through‐going fractures, where the extent of precipitation increased with increasing calcite content. Precipitates were strongly localized within fracture networks due to mineral, geochemical, and structural heterogeneities and generally concentrated in smaller apertures where rock:water ratios were highest. The combination of elevated fluid saturation and reactive surface area created in freshly activated fractures drove near‐immediate mineral precipitation that led to an 80% permeability reduction and significant flow obstruction in the most reactive core. While most previous studies have focused on mixing‐induced precipitation, this work demonstrates that fluid–rock interactions can trigger precipitation‐induced permeability alterations that can initiate or mitigate risks associated with subsurface energy systems.