Abstract: The present disclosure provides a 3D structured inorganic nanoscale product and a printing method and application thereof. The printing method includes the following steps: (1) mixing an inorganic nanocrystal and a photosensitive crosslinkable compound in a solvent to obtain a printing solution; wherein the inorganic nanocrystal has a ligand containing a carbon-hydrogen bond on the surface thereof; (2) obtaining a 3D printed product using laser 3D printing; wherein the photosensitive crosslinkable compound is a nitrene-based photosensitive crosslinking agent and/or a carbene-based photosensitive crosslinking agent. The method achieves the printing of semiconductor materials, metals, and metal oxide materials with submicron precision and any complex 3D structures through light-triggered chemical covalent bonding of ligands. The nanomaterials in the printed 3D structures retain their inherent morphology, and electrical and optical properties.