The stability of the Pr valence and the role of the Pr−O bonds in the Pr-based cobaltite Pr0.50Sr0.50CoO3 across the unexpected magnetostructural transition were studied at low temperature. A complete X-ray absorption spectroscopy study as a function of temperature revealed the absence of charge transfer from Pr to Co sites and of spin-state transitions in the Co ions despite the strong Pr−O hybridization. Theoretical calculations support the experimental data.