Spinel LiMn2O4 films were obtained by spin-coating the lithium/manganese acetates-containing precursor solution on a Pt-coated silicon substrate. The effect of chitosan addition in the acetates-containing precursor solution on the formation of the LiMn2O4 films was investigated by TG/DTA, FT-IR spectroscopy, glancing-angle XRD and cyclic voltammetry. It was demonstrated that the addition of chitosan is very beneficial to the deposition of a single-phase LiMn2O4 film due to the fact that chitosan is able to chelate with lithium/manganese ions and form a stable complex compound. Moreover, the electrochemical measurements also showed that the deposited LiMn2O4 film from the chitosan-added precursor solution exhibits a higher discharge capacity of 134mAh/g at 1C and a better rate performance (86.4% of the discharge capacity at 1C can be maintained when the discharge rate increases from 1 up to 8C) in comparison with one from the chitosan-free solution.