The mean oxidation state of cationic elements in Pr2NiO4+delta was studied using XANES measurements versus temperature in air. Unexpectedly, praseodymium is solely found as Pr3+ while Pr4+ was also foreseeable. Pr3+ cation is well accommodated in the large rare-earth site with the nine-fold coordination in this K2NiF4 - T-type structure; conversely, the small size of the Pr4+ cation seems not compatible with this site. Moreover, XANES measurements show a progressive decrease of the mean oxidation state of nickel ions when the temperature increases. It is directly correlated to the decrease of the oxygen over-stoichiometry of the material evidenced by TGA measurements.