The separation of styrene and ethylbenzene mixtures is industrially important and is currently performed in highly energy-intensive vacuum distillation columns. The primary objective of our investigation is to offer an energy-efficient alternative for selective adsorption of styrene by a flexible metal-organic framework, DynaMOF-100. The structural transformation of DynaMOF-100 is specifically triggered on inclusion of styrene within the framework; this structural transformation is reversible. The styrene/ethylbenzene adsorption selectivity, originated as an outcome of the framework flexibility, is found to be much superior to the only two MOFs yet reported, serving styrene/ethylbenzene separation purpose.