It is known that solid-state reaction in high-pressure oxygen can stabilize high-oxidation phases of Y-Ba-Cu-O superconductors in powder form. We extend this superoxygenation concept of synthesis to thin films which, due to their large surface-to-volume ratio, are more reactive thermodynamically. Epitaxial thin films of YBa2Cu3O 7−δ grown by pulsed laser deposition are annealed at up to 700 atm O2 and 900 • C, in conjunction with Cu enrichment by solid-state diffusion. The films show clear formation of Y2Ba4Cu7O 15−δ and Y2Ba4Cu8O16 as well as regions of YBa2Cu5O 9−δ and YBa2Cu6O 10−δ phases, according to scanning transmission electron microscopy, x-ray diffraction and x-ray absorption spectroscopy. Similarly annealed YBa2Cu3O 7−δ powders show no phase conversion. Our results demonstrate a novel route of synthesis towards discovering more complex phases of cuprates and other superconducting oxides.