In this study, nanostructured ceria (CeO2) films are deposited on Si(100) and ITO coated glass substrates by pulsed DC magnetron sputtering using a CeO2 target. The influence on the films of using various gas ambients, such as a high purity Ar and a gas mixture of high purity Ar and O2, in the sputtering chamber during deposition are studied. The film compositions are studied using XPS and SIMS. These spectra show a phase transition from cubic CeO2 to hexagonal Ce2O3 due to the sputtering process. This is related to the transformation of Ce4+ to Ce3+ and indicates a chemically reduced state of CeO2 due to the formation of oxygen vacancies. TGA and electrochemical cyclic voltammetry (CV) studies show that films deposited in an Ar atmosphere have a higher oxygen storage capacity (OSC) compared to films deposited in the presence of O2. CV results specifically show a linear variation with scan rate of the anodic peak currents for both films and the double layer capacitance values for films deposited in Ar/O2 mixed and Ar atmosphere are (1.6 ± 0.2) x 10-4 F and (4.3 ± 0.5) x 10-4 F, respectively. Also, TGA data shows that Ar sputtered samples have a tendency to greater oxygen losses upon reduction compared to the films sputtered in an Ar/O2 mixed atmosphere.