Because organic donor/acceptor blending systems play critical roles in ambipolar transistors, photovoltaics, and light-emitting transistors, it is highly desirable to precisely tailor the stacking of cocrystals toward different intrinsic structures and physical properties. Here, we demonstrated that the structure-stacking modes and electron-transport behaviors of coronene-F4TCNQ cocrystals (1:1) can be tuned through the solvent accommodation. Our results clearly show that the solvent accommodation not only enlarges the inner mixed packing (...DAD···) distances, leading to the depressed short-contact interactions including the side-by-side and face-by-face intermolecular interactions, but also switches off electron-transport behavior of coronene-F4TCNQ cocrystals (1:1) in ambient atmosphere.