An extensive theoretical study of the thermal decomposition of alkyl- and phenylureas, which are widely used in the pesticides, pharmaceuticals, and materials industries, has been carried out using electronic structure calculations and reaction rate theories. Enthalpies of formation and bond dissociation energies (BDE) of 11 urea derivatives have been calculated using different levels of theory (CBS-QB3, CCSD(T)/CBS//M06-2X/6-311++G(3df,2pd), and CBS-QM062X) according to the size of the system. Potential energy surfaces for the unimolecular decomposition pathways of these urea derivatives were also systematically computed for the first time. Several pericyclic reactions can be envisaged, as a function of the size and the nature of the N substituents, and all of these pathways were explored. Our calculations show that these compounds are solely decomposed by four-center pericyclic reactions, yielding substituted isocyanates and amines, and that initial bond fissions are not competitive. Based on the set of urea derivatives studied, a new reaction rate rule for their thermal decomposition was defined and involves the nature of the transferred H atom (primary or secondary/alkyl or benzyl) and the nature of the N-atom acceptor (primary, secondary, or tertiary). This new reaction rate rule allows us to determine the product branching ratios in the thermal decomposition of a given urea derivative and its total rate of decomposition. Applications on urea derivatives used in the chemical industry are presented and illustrate the usefulness of this new rate rule that allows to predict the previously unknown thermal decomposition kinetics of a large number of these compounds.