Hollow nanoparticles featuring tunable structures with spatial and chemical specificity are of fundamental interest. However, it remains a significant challenge to design and synthesize asymmetric nanoparticles with controllable topological hollow architecture. Here, a versatile kinetics‐regulated cooperative polymerization induced interfacial selective superassembly strategy is demonstrated to construct a series of asymmetric hollow porous composites (AHPCs) with tunable diameters, architectures and components. The size and number of patches on Janus nanoparticles can be precisely manipulated by the precursor and catalyst content. Notably, AHPCs exhibit excellent photothermal conversion performance under the irradiation of a near infrared (NIR) laser. Thus, AHPCs are utilized as NIR light‐triggered nanovehicles and cargos can be controllably released. In brief, this versatile superassembly approach offers a streamlined and powerful toolset to design diverse asymmetric hollow porous composites.