The ability to engineer microscale and nanoscale morphology upon metal nanowires (NWs) has been essential to achieve new electronic and photonic functions. Here, this study reports an optically programmable Plateau−Rayleigh instability (PRI) to demonstrate a facile, scalable, and high-resolution morphology engineering of silver NWs (AgNWs) at temperatures <150 °C within 10 min. This has been accomplished by conjugating a photosensitive diphenyliodonium nitrate with AgNWs to modulate surface-atom diffusion. The conjugation is UV-decomposable and able to form a cladding of molten salt-like compounds, so that the PRI of the AgNWs can be optically programmed and triggered at a much lower temperature than the melting point of AgNWs. This PRI self-assembly technique can yield both various novel nanostructures from single NW and largearea microelectrodes from the NW network on various substrates, such as a nanoscale dot-dash chain and the microelectrode down to 5 μm in line width that is the highest resolution ever fabricated for the AgNW-based electrode. Finally, the patterned AgNWs as flexible transparent electrodes were demonstrated for a wearable CdS NW photodetector. This study provides a new paradigm for engineering metal micro-/nanostructures, which holds great potential in fabrication of various sophisticated devices.