Flash vacuum pyrolysis (FVP) of aryl 2-(allyloxy)benzoates 5 and of the corresponding aryl 2-(allylthio)benzoates 6 at 650 °C, gives dibenzofurans 19 and dibenzothiophenes 20, respectively. The mechanism involves generation of phenoxyl (or thiophenoxyl) radicals by homolysis of the O-allyl (or S-allyl) bond, followed by ipso attack at the ester group, loss of CO₂ and cyclisation of the resulting aryl radical. Synthetically, the procedure works well for p-substituted substrates, which lead to 2-substituted dibenzofurans 19b–f (73–90%) and dibenzothiophenes 20b–c (90–94%). Little selectivity is shown in the cyclisation of m-substituted substrates and competing interactions of the radical with the substituent—and ipso-attack—complicate the pyrolyses of o-substituted substrates. FVP of related radical precursors including 2-(allyloxy)phenyl benzoates 43 gave no dibenzofurans, whereas 2-(allyloxy-5-methyl)azobenzene 44 gave a much reduced yield. No carbazoles were obtained by FVP of 4-methylphenyl 2-(allylamino)benzoate 42.