Abstract Fifteen perovskite manganites Sr1−xPrxMnO3, x=0.1−0.6 in steps as fine as 0.025, have been synthesized by solid state methods and their crystal structures determined using synchrotron X-ray powder diffraction. At room temperature two first order phase transitions associated with changes in the orbital ordering and the tilting of the corner shared MnO6 octahedra are evident c u b i c / P m 3 ¯ m ⟹ x ≈ 0.15 t e t r a g o n a l / ( I 4 / m c m ) ⟹ x ≈ 0.45 o r t h o r h o m b i c / I m m a , with two phase regions associated with both transitions. Heating the Pr rich oxide Sr0.5Pr0.5MnO3 provides a rare example where chemical pressure and temperature result in a different sequence of transitions Imma– R 3 ¯ c – P m 3 ¯ m , reflecting the importance of the Pr 4f electrons. X-ray absorption near-edge structure (XANES) measurements at the Mn K and Pr L3 edges show the valence state of the Mn linearly decreases with increasing Pr content whereas the Pr remains +3 across the entire series. Magnetic susceptibility measurements for selected samples are presented.