Ultraviolet irradiation of 2,3-dihydro-2,6-dimethyl-4-pyrone in aqueous solution leads to the regiospecific and stereoselective formation of three cis–anti–cis photodimers of the cyclobutane type, i.e0., octahydro-2,7-8a,8b-tetramethylcyclobuta[1,2-b:4,3-b′]dipyran-4,5-diones, whose structures have been established by chemical and spectroscopic methods, including studies of nuclear Overhauser effects in the proton magnetic spectrum of one of them. The dimers undergo photointerconversion, and it is proposed that this process involves photoreversion to monomer and that the reversibility of the dimerization reaction may be a factor in determining the regiochemistry and stereochemistry of the photodimers. A bisdehydro product prepared from the dimers of the dihydropyrone has been shown to undergo photocleavage to 2,6-dimethyl-4-pyrone, and it is proposed that reversibility may also be a factor affecting the course of the photodimerization of this pyrone.