Copper nanowires (Cu NWs) have become a promising material for flexible transparent conductive electrodes (FTCEs) owing to their outstanding transparency and conductivity properties. In this work, ultralong Cu NWs with an average length over 250 mu m and a diameter of around 50 nm (aspect ratio similar to 5000) were synthesized in a water/polyhydric alcohol cosolvent. The effects of polyhydric alcohols (including ethanol, ethylene glycol, and glycerol) on the aspect ratio of Cu NWs were investigated. The diameter of Cu NWs decreased with the increased number of hydroxyl groups of polyhydric alcohols. In addition, the capping ligands (oleylamine and oleic acid) and glucose also exhibit important effects on the dispersity and morphology of Cu NWs. The ultralong Cu NW-based poly(dimethylsiloxane) (PDMS) FTCEs exhibit high performance with a low sheet resistance of 92.1 Omega sq(-1) at a transmittance of 91.524%. Inspired by the stretchable ability of PDMS, wearable sensors were fabricated to detect the movement of the finger joint through the chronoamperometry method. The prepared sensors exhibit high sensitivity and a fast response time. The excellent performance of FTCEs and wearable sensors suggests that the ultralong Cu NWs have a bright future in the application of the next generation of flexible optoelectronic devices.