Abstract The chemistry of lanthanides (Ln=La–Lu) is dominated by the low‐valent +3 or +2 oxidation state because of the chemical inertness of the valence 4f electrons. The highest known oxidation state of the whole lanthanide series is +4 for Ce, Pr, Nd, Tb, and Dy. We report the formation of the lanthanide oxide species PrO 4 and PrO 2 + complexes in the gas phase and in a solid noble‐gas matrix. Combined infrared spectroscopic and advanced quantum chemistry studies show that these species have the unprecedented Pr V oxidation state, thus demonstrating that the pentavalent state is viable for lanthanide elements in a suitable coordination environment.