This study develops the reaction pathway map for the unimolecular decomposition of catechol, a model compound for various structural entities present in biomass, coal, and wood. Reaction rate constants at the high-pressure lit-nit are calculated for the various possible initiation channels. It is found that catechol decomposition is initiated dominantly via hydroxyl H migration to a neighboring ortho carbon bearing an H atom. We identify the direct formation of o-benzoquinone to be unimportant at all temperatures, consistent with the absence of this species from experimental measurements. At temperatures higher than 1000 K, water elimination through concerted expulsion of a hydroxyl OH together with an ortho H becomes the most significant channel. Rice - Ramsperger-Kassel-Marcus simulations are performed to establish the branching ratio between these two important channels as a function of temperature and pressure. All unimolecular routes to the reported major experimental products (CO, 1,3-C4H6 and cyclo-C5H6) are shown to incur large activation barriers. The results presented herein should be instrumental in gaining a better understanding of the decomposition behavior of catechol-related compounds.