The redox properties of praseodymia have been compared to those of ceria using temperature‐programmed desorption (TPD) of O2 from films prepared by vapor deposition onto an α‐Al2O3(0001) support, in order to assess the potential for praseodymia as an oxygen‐storage component in three‐way catalysts. Desorption of O2 was observed between 700 and 1000 K, and diffraction measurements confirmed that the films change from Pr6O11 to Pr2O3 in this temperature range. However, once reduced, the films could not be reoxidized by exposures to O2 in the vacuum system. Evidence was found for oxygen transfer from Pr6O11 to supported Rh particles. Following CO adsorption on Rh particles deposited onto Pr6O11 film, significant amounts of CO2 were observed in TPD until the film was completely reduced to Pr2O3. Following deposition of Rh particles onto Pr6O11, the oxygen desorption curves became identical to those normally observed for Rh. These results are compared with similar measurements performed on ceria films and the implications for automotive, emission‐control catalysis are discussed.