The interplay between structural and electronic phases in iron-based superconductors is a central theme in the search for the superconducting pairing mechanism. While electronic nematicity is competing with superconductivity, the effect of purely structural orthorhombic order is unexplored. Here, using x-ray diffraction and angle-resolved photoemission spectroscopy, we reveal a structural orthorhombic phase in the electrondoped iron-pnictide superconductor Pr4Fe2As2Te0.88O4 (T-c = 25 K), which is distinct from orthorhombicity in the nematic phase in underdoped pnictides. Despite the high electron doping we find an exceptionally high orthorhombic onset temperature (T-ort similar to 250 K), no signatures of phase competition with superconductivity, and absence of electronic nematic order as the driving mechanism for orthorhombicity. Combined, our results establish a high-temperature phase in the phase diagram of iron-pnictide superconductors and impose strong constraints for the modeling of their superconducting pairing mechanism.