Here we show how the electromechanical properties of silicon nanowires (NWs) are modified when they are subjected to extreme mechanical deformations (buckling and buckling mode transitions), such as those appearing in flexible devices. Flexible devices are prone to frequent dynamic stress variations, especially buckling, while the small size of NWs could give them an advantage as ultra-sensitive electromechanical stress sensors embedded in such devices. We evaluated the NWs post-buckling behavior and the effects of buckling mode transition on their piezoresistive gauge factor (GF). Polycrystalline silicon NWs were embedded in SiO2 microbridges to facilitate concurrent monitoring of their electrical resistance without problematic interference, while an external stylus performed controlled deformations of the microbridges. At points of instability, the abrupt change in the buckling configuration of the microbridge corresponded to a sharp resistance change in the embedded NWs, without altering the NWs' GF. These results also highlight the importance of strategically positioning the NW in the devices, since electrical monitoring of buckling mode transitions is feasible when the deformations impact a region where the NW is placed. The highly flexible NWs also exhibited unusually large fracture strength, sustaining tensile strains up to 5.6%; this will prove valuable in demanding flexible sensors. © 2010 IOP Publishing Ltd.