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Next‐generation lithography techniques based on the self‐assembly of block copolymers (BCPs) are promising methods for high‐resolution pattering. BCPs with a high incompatibility (high‐χ), such as polystyrene‐polydimethylsiloxane (PS‐PDMS), show encouraging results in terms of resolution. In the strong segregation regime, the high diffusive energy barrier of PS‐PDMS excessively reduces the self‐assembly kinetics; this is why solvent–vapor annealing is typically adopted to shorten the self‐assembly time. Plasticizers are generally used to reduce the glass transition temperature (T_g) of polymers. In this study, commercial plasticizers such as dioctylsebacate and diisooctyl adipate are blended with PS‐PDMS polymers, and their influence on the self‐assembly process is investigated. The intrinsic PS selectivity of the plasticizers brings the BCP to form PS‐PDMS micelles, which results in highly ordered self …