Spectroscopic (XPS, ToF-SIMS) and microscopic (SEM, AFM) analytical methods have been applied to iron oxide (∼Fe2O3) using a thin film approach to bring new insight into the aging mechanisms of conversion-type anode materials for lithium-ion batteries. The results show that repeated lithiation/delithiation causes both chemical and morphological modifications affecting the electrochemical performance. The SEI layer formed by reductive decomposition of the electrolyte remains stable in composition (mostly Li2CO3) but irreversibly thickens upon multicycling. Irreversible swelling of the material accompanied by penetration of the SEI layer and accumulation of non-deconverted material in the bulk of the oxide thin film occurs upon repeated conversion/deconversion. After initial pulverization of the thin film microstructure, grain growth and aggregation are promoted by multicycling. This leads to capacity increase in the first few cycles, but upon further cycling volume expansion and accumulation of non-deconverted material lead to deterioration of the electrode performances.