An order–order transition (OOT) in the sequence of a hexagonally arranged core–shell cylinder to a double‐hexagonally arranged dot in polystyrene‐block‐poly(butadiene)‐block‐poly(2‐vinylpyridine) (SBV) triblock copolymer thin films is reported to be induced upon exposure to a solvent vapor that is strongly selective for the two end blocks. These two kinds of hexagonally arranged structures could form when the film thickness is 44, 123, and 223 nm. When the film thickness is decreased to 13 nm, the ordered structure is absent. The sizes of the core–shell cylinder structures formed with the same annealing time in films of different thickness are compared to address the effects of film thickness on the phase structure. The mechanism is analyzed from the total surface area of the blocks and the effective interaction parameter in the solvent vapor.
