This work presents a stress characterization of crystalline Si electrodes using micro-Raman spectroscopy. First, the phase heterogeneity in the c-Si electrodes after initial lithiation was investigated by scanning electron microscopy (SEM) and other complementary techniques. A surprising three-phase layer structure, with a-LixSi (x = 2.5), c-LixSi (x = 0.3-2.5), and c-Si layers, was observed, and its origin was attributed to the electro-chemo-mechanical (ECM) coupling effect in the c-Si electrodes. Then, a Raman scan was performed to characterize stress distribution in lithiated c-Si electrodes. The results showed that the maximum tensile stress occurred at the interface between c-LixSi and c-Si layers, indicating a plastic flow behavior. The yield stress increased with total lithium charge, and the relationship showed consistency with a prior multibeam optical sensor (MOS) study. Lastly, stress distribution and structural integrity of the c-Si electrodes after initial delithiation and further cycling were studied, and a comprehensive picture of the failure mechanism of the c-Si electrode was obtained.