Hierarchical superstructures in nano/microsize have attracted great attention owing to their wide potential applications. Herein, a self-templated strategy is presented for the synthesis of a spherical superstructure of carbon nanorods (SS-CNR) in micrometers through the morphology-preserved thermal transformation of a spherical superstructure of metal-organic framework nanorods (SS-MOFNR). The self-ordered SS-MOFNR with a chestnut-shell-like superstructure composed of 1D MOF nanorods on the shell is synthesized by a hydrothermal transformation process from crystalline MOF nanoparticles. After carbonization in argon, the hierarchical SS-MOFNR transforms into SS-CNR, which preserves the original chestnut-shell-like superstructure with 1D porous carbon nanorods on the shell. Taking the advantage of this functional superstructure, SS-CNR immobilized with ultrafine palladium (Pd) nanoparticles (Pd@SS-CNR) exhibits excellent catalytic activity for formic acid dehydrogenation. This synthetic strategy provides a facile method to synthesize uniform spherical superstructures constructed from 1D MOF nanorods or carbon nanorods for applications in catalysis and energy storage.