Tuning of crystal structures and shapes of submicrometer-sized noble metals have revealed fascinating catalytic, optical, electrical, and magnetic properties that enable developments of environmentally friendly and durable nanotechnological applications. Several attempts have been made to stabilize Au, knowing its extraordinary stability in its conventional face-centered cubic (fcc) lattice, into different lattices, particularly to develop Au-based catalysis for industry. Here, we report the results from scanning X-ray diffraction microscopy (SXDM) measurements on an ambient-stable penta-twinned bipyramidal Au microcrystallite (about 1.36 μm in length and 230 nm in diameter) stabilized in noncubic lattice, exhibiting catalytic properties. With more than 82% of the crystal volume, the majority crystallite structure is identified as body-centered orthorhombic (bco), while the remainder is the standard fcc. A careful analysis of the diffraction maps reveals that the tips are made up of fcc, while the body contains mainly bco with very high strain. The reported structural imaging technique of representative single crystallite will be useful to investigate the growth mechanism of similar multiphase nano- and micrometer-sized crystals.