Copper tetracyanoquinodimethane (CuTCNQ) has been investigated around 40 years as a representative bistable material. Meanwhile, micro/nanostructures of CuTCNQ is considered as the prototype of molecular electronics, which have attracted the world's attention and shown great potential applications in nanoelectronics. In this review, methods for synthesis of CuTCNQ micro/nanostructures are first summarized briefly. Then, the strategies for controlling morphologies and sizes of CuTCNQ micro/nanostructures are highlighted. Afterwards, the devices based on these micro/nanostructures are reviewed. Finally, an outlook of future research directions and challenges in this area is presented.