Hollow multishelled structures (HoMSs), an emergent solid-state material family featuring multiple shells separated by internal cavities, are gaining intensive interest in applications exercising their temporal-spatial ordering or dynamic smart behavior. Although the assembled shell structures and tailored building blocks on the nanometer/micrometer (nano/micro) scale have been extensively studied, understanding of the interplay among the different degrees of freedom (i.e., charge, spin, orbital, and lattice) in HoMSs remains in its infancy. In this review, the new trend in HoMS chemistry regarding the influence of interactions among electron-orbital-lattice on the attractive physicochemical properties of HoMSs is investigated. By demonstrating pioneering work regulating the optical, electronic, catalytic, and magnetic properties of HoMSs, we uncover perfor-mance enhancements from an atomic perspective. Hopefully, the new research outlook in HoMSs inspires innovative prospects for the rational design of HoMS materials by using alternative degrees of freedom and/or tailoring their mutual interactions.