The structural colored balloons (SCBs) consisting of polymer microcapsules showed several structural colors developed by optical thin-layer interference. The SCBs were prepared using a mixture of low- and high-molecular-weight polystyrene to give solvent responsiveness. When the surrounding solvent was transferred from water to the acetone/water mixture using a flow cell, the SCBs swelled at first and shrunk subsequently. The gradual color change of the SCBs was observed along with the size change. The color change accompanying the size change was successfully reproduced by assuming that the total amount of polymer in the thin film does not change. The swelling rate was rationalized by the diffusion of solvent through the shell polystyrene film to the inside of the balloons.