The three-dimensionally porous MnO thin-film electrodes supported on nickel foam and stainless steel substrates were prepared by the improved electrostatic spray deposition (ESD) technique. X-ray diffraction, scanning electron microscopy, and galvanostatic cell cycing are employed to characterize the structures and electrochemical performance of the MnO thin-film electrodes. The results show that these as-prepared MnO thin-film electrodes have a special three dimensional porous network structure and also have stable cycling performance with a reversible capacity of over 850 mAh g−1 after 50 cycles at a current density of 80mAg−1. The MnO thin-film deposited on the nickel foam shows the highest initial columbic efficiency (83.9%), the lowest initial capacity loss (14.2%), and the best rate performance with a high capacity of 498.4 mAh g−1 at a current density of 1200mAg−1. The experimental results suggest that such the MnO thin-film with a special structure is a promising anode material for lithium-ion batteries.