High-entropy fluorite oxides offer exceptional tunability of structure and functionality through controlled multi-cation substitution. In this work, Ce-Zr-Pr-Sm-Eu-based high-entropy oxides, with systematically varied Pr content, were synthesized using a modified sol–gel citrate method to investigate the influence of Pr incorporation on lattice structure, defect formation, and photocatalytic performance. All compositions crystallized in a single-phase cubic fluorite structure, where increasing Pr concentration induced gradual lattice expansion and microstrain due to the substitution of larger Pr³⁺ ions. Morphological and surface analyses revealed porous nanostructures at moderate Pr levels, while excessive Pr promoted densification and reduced surface accessibility. Spectroscopic studies confirmed the coexistence of Pr³⁺/Pr⁴⁺ and Ce³⁺/Ce⁴⁺ redox couples, strong 4f–2p orbital hybridization, and enhanced defect-related electronic states that narrowed the optical bandgap. The optimized Pr-doped composition exhibited almost 100% degradation of methylene blue under UV light over 30 min, untypical for semiconductors with a narrower bandgap, and is enabled by efficient charge separation and redox cycling between Ce and Pr centers.