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We have designed a series of high-χ alternating copolymers (ACPs), in which the polar and apolar repeating units are four hydroxyl teams and alkyl chains, respectively. Cautious coarse-grained molecular characteristics (CG-MD) simulations demonstrate that these ACPs can form a variety of mesophases, including lamellae, perforated lamellae, and hexagonally packed cylinders. All of the domain periods of those mesophases are smaller compared to 5 nm, and also the littlest domai