The redox targeting reaction of Li+-storage materials with redox mediators is the key process in redox flow lithium batteries, a promising technology for next-generation large-scale energy storage. The kinetics of the Li+-coupled heterogeneous charge transfer between the energy storage material and redox mediator dictates the performance of the device, while as a new type of charge transfer process it has been rarely studied. Here, scanning electrochemical microscopy (SECM) was employed for the first time to determine the interfacial charge transfer kinetics of LiFePO4/FePO4 upon delithiation and lithiation by a pair of redox shuttle molecules FcBr2+ and Fc. The effective rate constant keff was determined to be around 3.70-6.57 × 10-3 cm/s for the two-way pseudo-first-order reactions, which feature a linear dependence on the composition of LiFePO4, validating the kinetic process of interfacial charge transfer rather than bulk solid diffusion. In addition, in conjunction with chronoamperometry measurement, the SECM study disproves the conventional "shrinking-core" model for the delithiation of LiFePO4 and presents an intriguing way of probing the phase boundary propagations induced by interfacial redox reactions. This study demonstrates a reliable method for the kinetics of redox targeting reactions, and the results provide useful guidance for the optimization of redox targeting systems for large-scale energy storage.