Tetrakis(trimethylsilyl)-p-benzoquinone (1) was obtained by oxidation of hexakis(trimethylsilyl)hydroquinone with pyridinium chlorochromate. X-Ray crystallographic analysis of 1 showed the quinone ring was distorted into a chair form by steric hindrance. Photolysis resulted in a rearrangement of the quinone ring and produced a ketene derivative.