Self‐assembled bottlebrush block copolymers (BBCPs) offer a vibrant, eco‐friendly alternative to traditional toxic pigments and dyes, providing vivid structural colors with significantly reduced environmental impact. Scaling up the synthesis of these polymers for practical applications has been challenging with conventional batch methods, which suffer from slow mass and heat transfer, inadequate mixing, and issues with reproducibility. Precise control over molecular weight and dispersity remains a significant challenge for achieving finely tuned color appearances. Here, we present an alternative strategy to overcome the challenges by integrating a rapid continuous flow technique with an in‐line self‐assembly procedure. This strategy enables the rapid, stable and large‐scale synthesis of narrow‐dispersed BBCPs, exceeding 2 kg/day, a significant improvement over conventional gram‐scale methods. Furthermore, precise control over the degree of polymerization is achieved with an unprecedented interval accuracy of four repeat units. This level of precision enables refined color calibration in the resulting photonic pigments, effectively eliminating the need for labor‐intensive and costly multiple batch syntheses.
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