Exo-templating introduces a novel strategy for guiding multicomponent self-assembly through external molecular scaffolds.The approach leverages a charged ring molecule to direct the assembly landscape by interacting with specific building block groups.By modulating kinetic pathways, exo-templating enhances the efficiency and reduces kinetic hindrance in forming nanospheres.Exo-templating destabilizes off-path intermediates, facilitating the assembly of well-defined structures with improved kinetics.This methodological innovation brings a catalytic paradigm to supramolecular chemistry, simplifying complex assembly processes.The external positioning of the template in exo-templating simplifies downstream processing compared to traditional endo-templating.The study emphasizes the strategic design of building blocks with specific interaction sites for efficient pseudorotaxane formation.Exo-templating offers a scalable approach to overcoming combinatorial complexities in forming artificial nanostructures.The kinetic modulation by the exo-templating ring accelerates the formation of desired structures without altering thermodynamic preferences.The generalizability of exo-templating hints at broader applications across various self-assembly systems beyond Pd₁₂L₂₄ nanospheres.