We have conducted X-ray absorption spectroscopy study for perovskite cobaltite Pr1-xSrxCoO3 (0 ≤ x ≤ 0.5) to understand Sr doping effect and magnetocaloric measurement for Pr0.5Sr0.5CoO3 to reveal the origin of magnetic anomaly at around 110 K. The extended X-ray absorption fine structure (EXAFS) measurements at the Co K-edge suggest that the average valence value of Co ions increases, the interatomic distance of Co–O bonding decreases, and the local distortion of CoO6 octahedron increases as Sr is doped in PrCoO3. The interatomic distance of Co–O bonding shrinks more greatly for the larger doping region. No temperature dependent electronic and structural changes were observed from Co K-edge X-ray absorption spectra in the whole thermal range studied (17–300 K). The magnetocaloric effect of Pr0.5Sr0.5CoO3 indicates the change of magnetic structure at 110 K.