The emergence of single molecule-based super-localization and super-resolution microscopy imaging techniques have dramatically improved our ability to reveal more detailed molecular dynamics and structural information and led to new discoveries in chemical and biological research that were previously unattainable with conventional diffraction-limited techniques.However,the current super-resolution chemical imaging techniques still lack several critical abilities,including insufficient axial resolution and the difficulty of imaging more complex three-dimensional(3D)nanomaterials.In seeking to circumvent these limitations,we are developing 3D super-resolution imaging for understanding molecular dynamics(including diffusion,adsorption,and chemical conversion,as well as their coupling)in nanopores at the single-molecule level under operando conditions.Highly tunable core-shell structures with well-defined geometry and manageable complexity have been designed and synthesized,and then visualized under our optical imaging system.Single molecule trajectories with nanometer resolution have been acquired to elucidate the effects of pore size,length,orientation,and surface ligands on molecular transport.New experimental insights on transport in nanoscale confinement acquired with the model core-shell porous structures can be generalized to guide the development of porous materials for heterogeneous catalysis and analytical separations.