The thermal decomposition reactions of 2(3H) and 2(5H) furanones and their methyl derivatives are explored. Theoretical calculations of the barriers, reaction enthalpies, and the properties of these and intermediate species are reported using the composite model chemistry CBS-QB3 and also the functional M06-2X allied to the 6-311++G(d,p) basis set. Thus, the bond dissociation enthalpies, ionization energies, and unimolecular chemical kinetic rate constants in the high-pressure limit were computed. We show that flow reactor experiments that intimated that heating the 2(3H) furanone converts it to the isomeric 2(5H) furanone occurs via a 1 → 2 H-transfer reaction to an open ring ketenoic aldehyde. The latter can then ring close to the other isomeric structure. The final products acrolein and carbon monoxide are only formed from 2(3H), and acrolein will further decompose to ethylene and CO. Comparable channels explain the interconversion of 5-methyl-2(3H) furanone to its 2(5H) isomer and to the formation of methyl vinyl ketone and CO. The influence of the methyl group at other positions on the ring is hardly of significance except in the case of 5-methyl-2(5H) furanone where a hydrogen atom transfer from the methyl group leads to the formation of a doubly unsaturated carboxylic compound, 2,4-pentadienoic acid. Studies of the UV photolysis of the parent compounds in both low-temperature inert argon matrices and in solution are broadly in accord with the thermal findings insofar as product formation is concerned and with our theoretical calculations. The dominant features of the early decomposition chemistry of these compounds are simple hydrogen transfer and simultaneous ring opening reactions, which do however result in some quite unusual species.