We report here a new polymorph of cocrystal CuQ2-TCNQ that shows an oriented single-crystal-to-single-crystal phase transition along its a-axis at ambient conditions. Upon mechanical stimulation, it converts into another polymorph accompanied by almost doubling its length and halving its thickness. Our crystallographic studies indicate the dramatic changes in crystal dimensions resulted from the prominent changes of molecular stacking patterns. A reasonable mechanism for the phenomenon was proposed on the basis of the structural, microscopic, and thermal analysis.