Borides are a family of materials with valuable properties for various applications. Their diverse structures and compositions, yet disparity in the constituent chemical elements for the known compounds, give elemental substitutions for prototypes great potential for material discovery. To explore uncharted material compositional space, we develop a workflow that joins high-throughput crystal structure prediction and automated diffraction pattern matching to discover new compounds with significant prediction and synthesis hurdles. Utilizing the workflow, we explore the empty Mg−Fe−B ternary compositional space, previously uncharted largely due to the immiscibility of Mg and Fe, as a paradigm. A total of 275 ternary boride prototypes are classified, using which we predict 23 (158) stable and metastable ternary phases within 50 (200) meV/atom above the convex hull. We identify Gd 2 (FeB) 7 -type Mg 2 Fe 7 B 7 and ZrCo 3 B 2 -type MgFe 3 B 2 to match previously unsolved experimental powder X-ray diffraction (PXRD) patterns. The discovered Mg 2 Fe 7 B 7 and related channeled structures feature mismatched Mg and (FeB) sublattice periods, for which we conduct structural analyses with respect to the PXRD. They are predicted to exhibit exceptionally fast superionic transport of Mg and outstanding electrochemical performance, which serve as post-Li-ion battery candidate electrode materials. This result opens a new avenue for borides' potential applications as electrode materials and fast ionic conductors. This work also portrays the map and landscape of ternary metal borides with similar chemical environments. With high efficiency, the prototype-and PXRD-assisted crystal structure prediction workflow opens a new avenue for exploring various material compositional spaces across the periodic table.