Flexible electronics attract research and commercial interests in last 2 decades for its flexibility, low cost, light weight and etc. To develop and improve the electro-mechanical properties of flexible electrodes is the most critical and important step. In this work, we have performed nanomechanical and electro-mechanical characterization of materials for flexible electrode applications, including metallic nanowires (NWs), indium tin oxide (ITO)-based and carbon nanotube (CNT)-based electrodes. First, we designed and developed four different testing platforms for nanomechanical and electro-mechanical characterization purpose. For the nano/sub-micro size samples, the micro mechanical devices can be used for uni-axial and bi-axial loading tests. For the macro size samples, the micro tester will be used for in situ monotonic tensile test, while the fatigue tester can be used for in situ cyclic tensile or bending testing purpose. Secondly, we have investigated mechanical behaviors of single crystalline Ni nanowires and single crystalline Cu nanowires under uni-axial tensile loading inside a scanning electron microscope (SEM) chamber. We demonstrated both size and strain-rate dependence on yield stress of single-crystalline Ni NWs with varying diameters (from 100 nm to 300 nm), and themolecular dynamics (MD) simulation helped to confirm and understand the experimental phenomena. Also, two different fracture modes, namely ductile and brittle-like fractures, were found in the same batch of Cu nanowire samples. Finally, we studied the electro-mechanical behaviors of flexible electrodes in macro scale. We reported a coherent study integrating in situ electro-mechanical experiments and mechanics modeling to decipher the failure mechanics of ITO-based and CNT-based electrodes under tension. It is believed that our combined experimental and simulation results provide some further insights into the important yet complicated deformation mechanisms for nanoscale metals and fracture mechanism for flexible electrodes applications.