Structural changes at electrode/electrolyte interface of a lithium cell were studied by X-ray reflectometry and two-dimensional model electrodes with a restricted lattice plane of LiMn2O4. The electrodes were constructed with an epitaxial film synthesized by the pulsed laser deposition method. The orientation of the film depends on the substrate plane; the (111), (110), and (100) planes of LiMn2O4 grew on the (111), (110), and (100) planes of the SrTiO3 substrates, respectively. The ex situ reflectometry indicated that a thin impurity layer covered the lattice plane of the as-grown film. The impurity layer was dissolved and a solid-electrolyte-interface-like phase appeared after the electrode was soaked into the electrolyte. A defect layer was formed in the (111) plane, whereas no density changes were detected for the other lattice planes. The in situ observation clarified that the surface reactivity depended on the lattice planes of the spinel; the defect layer at the (111) plane was stable during the electrochemical reaction, whereas a slight decrease in the film thickness was observed for the (110) plane. Our surface characterization of the intercalation electrode indicated that the surface structure changes during the pristine stage of the change-discharge processes and these changes are dependent on the lattice orientation of LiMn2O4.