Autocatalytic processes are important in many fields of science, including surface chemistry. A better understanding of its mechanisms may improve the current knowledge on heterogeneous catalysis. The thermally induced decomposition of eight different polycyclic aromatic hydrocarbons (PAHs) on a saturated monolayer of atomic oxygen on a Cu(100) surface is studied using temperature-programmed reaction spectroscopy (TPRS), X-ray photoelectron spectroscopy (XPS), and scanning tunneling microscopy (STM). 9-Bromo-heptahelicene decomposes autocatalytically in a narrow temperature range into CO2 and H2O, while non-halogenated heptahelicene decomposes into the same products but does not show autocatalytic behavior. Fixation of the hydrocarbon to the surface via the organometallic bond after elimination of the bromine is identified as a prerequisite for the autocatalytic reaction mechanism. Of all the hydrocarbons studied, only those being sterically overcrowded decompose autocatalytically. Such an observation can be explained by facile dehydrogenation of the overcrowded PAHs. The reaction of such hydrogen with oxygen creates vacancies in the oxygen layer which act as active sites and catalyze further decomposition.