Host–Guest Interactions Induced Self‐Assembly of Colloidal Micromotors with Regulated Motion Behavior

Abstract In recent years, extensive strategies are developed for designing and manufacturing micro‐ and nanomotors. However, the controlled assembly and motion modulation of self‐assembled micromotors via directional interactions remain challenging. While host–guest systems, particularly azobenzene‐β‐cyclodextrin (Azo‐β‐CD) interactions, are well‐established in supramolecular chemistry, their application to structurally guided micromotor assembly and motion control is underexplored. Here, this host–guest chemistry is integrated with established catalytic (Pt/H ₂ O ₂ ) and magnetic actuation mechanisms to achieve programmable assembly of micromotors with defined architectures. By using Azo‐ and β‐CD‐modified microspheres as host and guest components separately, spatially controlled assembly is demonstrated into structured motors. The motors have dual‐mode propulsion: chemically driven motion via Pt‐catalyzed decomposition of 10 wt.% H ₂ O ₂ and magnetic field‐directed locomotion. This synergy of supramolecular assembly and established actuation mechanisms advances structural precision in micromotor design, offering a platform for multifunctional systems. The findings bridge supramolecular chemistry and microengineering, providing a framework for applications requiring tailored architectures and multimodal motion, such as targeted drug delivery or environmental sensing.