Multicomponent colloidal nanostructures (MCNs) exhibit intriguing topologically dependent chemical and physical properties. However, there remain significant challenges in the synthesis of MCNs with high-order complexity. Here we show the development of a general yet scalable approach for the rational design and synthesis of MCNs with unique coaxial-like construction. The site-preferential growth in this synthesis relies on the selective protection of seed nanoparticle surfaces with locally defined domains of collapsed polymers. By using this approach, we produce a gallery of coaxial-like MCNs comprising a shaped Au core surrounded by a tubular metal or metal oxide shell. This synthesis is robust and not prone to variations in kinetic factors of the synthetic process. The essential role of collapsed polymers in achieving anisotropic growth makes our approach fundamentally distinct from others. We further demonstrate that this coaxial-like construction can lead to excellent photocatalytic performance over conventional core–shell-type MCNs.