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The past few years witnessed the rapid development of bottom-up synthesis strategies for preparing various nanostructures (i.e., nanoparticles, nanorods, nanowires, etc.) with distinct morphology-dependent properties. In this study, we reported a facile and efficient synthesis method for preparing anatase titanium dioxide (TiO 2 ) nanorings based on multiarm, starlike amphiphilic polystyrene- b -poly(acrylic acid) (PS- b -PAA) diblock copolymers as nanoreactors which were prepared via a sequential atom-transfer radical polymerization (ATRP) technique followed by the conversion of polystyrene- b -poly( tert -butyl acrylate) (PS- b -P t BA) to PS- b -PAA. The outer PAA block of nanoreactors possessed carboxylic acid groups which could coordinate with a titanium precursor followed by high-temperature calcination to form crystalline TiO 2 nanorings. The living nature of ATRP enabled the precise preparation of starlike diblock copolymer nanoreactors with a controlled length of each block (i.e., P t BA and PS), thereby tailoring the inner diameter and wall thickness of the resulting TiO 2 nanorings, which were inaccessible to conventional routes.