The invention relates to a single nanowire electrochemical device and an assembly and in-situ characterization method thereof. The method comprises the following steps of: dispersing nanowire anodes of vanadium oxide nanowires, and the like, nano film cathodes of HOPG (Highly Oriented Pyrolytic Graphite), and the like or nanowire cathodes of silicon nanowires, and the like and nano film anodes of LiCoO2, and the like on a substrate; respectively making metal electrodes at both ends of the nanowires and the nano films as current collectors by adopting technologies, such as PECVD (Plasma-Enhanced Chemical Vapor Deposition), and the like; then, depositing silicon nitride or spinning a photoresist on the metal current collectors as protection layers of the current collectors by adopting the PECVD technology, and the like; and finally, dispensing a polymer electrolyte on the surface of the substrate to finish the assembly of the single nanowire electrochemical device. In the invention, charging and discharging tests are carried out on the electrochemical device, then in-situ electrical transport performance tests, micro-domain Raman spectrum analysis, and the like are carried out on the single nanowire electrodes in different charging and discharging states, the direct relation among the electrical transport, the structure and the electrochemical performance of the nanowire electrode material is established, a platform is provided for battery diagnosis, and the like and a support power supply can be provided for the nano device.