The large amount of data collected during a typical operando X-ray absorption fine structure (XAFS) experiment and the interest to thoroughly investigate and comprehend a redox process occurring in a Li-ion battery need an advanced data analysis approach. In this context, multivariate curve resolution (MCR) has gained attention as chemometric technique that allows the identification of the number of the species and their existence range without any a priori information on the studied system. The call for an advanced data treatment is answered by a joint XAFS-MCR approach, able to unveil the local structural dynamics of the selected species, providing a quick and efficient data interpretation.