The nuclear and magnetic structures and properties of Sr0.65Pr0.35-xCexMnO3 (0.00 ≤ x ≤ 0.35) were investigated using a combination of synchrotron x-ray and neutron powder diffraction, along with magnetic and x-ray absorption near edge structure measurements. At room temperature, doping with Ce results in a transition from a tetragonal structure in I4/mcm to an orthorhombic one in Imma associated with the loss of long range orbital ordering. At low temperatures, we observe the formation of an orthorhombic Fmmm phase. XANES measurements demonstrate that the Ce exists as a mixture of Ce(3+) and Ce(4+).