The prototype high-entropy oxide (HEO) Y0.2La0.2Ce0.2Pr0.2Sm0.2O2−δ represents a particularly complex class of HEOs with significant anion sublattice entropy. The system takes either a fluorite or bixbyite-type crystal structure, depending on synthesis kinetics and thermal history. Here, we synthesize bulk ceramics and epitaxial thin films of Y0.2La0.2Ce0.2Pr0.2Sm0.2O2−δ and use diffraction to explore crystal symmetry and phase. Thin films exhibit the high symmetry fluorite phase, while bulk ceramics adopt the lower symmetry bixbyite phase. The difference in chemical ordering and observed symmetry between vapor-deposited and reactively sintered specimens suggests that synthesis kinetics can influence accessible local atomic configurations, i.e., the high kinetic energy adatoms quench in a higher-effective temperature, and thus higher symmetry structure with more configurational entropy. More generally, this demonstration shows that recovered HEO specimens can exhibit appreciably different local configurations depending on synthesis kinetics, with potential ramifications on macroscopic physical properties.