The insertion/extraction of lithium into/from various host materials is the basic process by which lithium-ion batteries reversible store charge. This process is generally accompanied by strain in the host material, inducing stress which can lead to capacity loss. Therefore, understanding of both the structural changes and the associated stress – investigated almost exclusively separate to date – is a critical factor for developing high-performance batteries. Here, we report an in situ method, which utilizes Raman spectroscopy in parallel with optical interferometry to study effects of varying charging rates (C-rates) on the structure and stress in a V2O5 thin film cathode. Abrupt stress changes at specific crystal phase transitions in the LiVO system are observed and the magnitude of the stress changes with the amount of lithium inserted into the electrode are correlated. A linear increase in the stress as a function of x in LixV2O5 is observed, indicating that C-rate does not directly contribute to larger intercalation stress. However, a more rapid increase in disorder within the LixV2O5 layers is correlated with higher C-rate. Ultimately, these experiments demonstrate how the simultaneous stress/Raman in situ approach can be utilized as a characterization platform for investigating various critical factors affecting lithium-ion battery performance.