Substituted benzyloxycarbonyloxyl radicals were generated by sensitised photolyses of benzyl oxime carbonates. EPR spectroscopy showed they ring closed exclusively by spiro-cyclisation onto the ipso-C-atoms of the aromatic rings. β-Scission of the alkoxycarbonyloxyls to CO2 and benzyloxyl radicals increasingly competed and became dominant above 270 K. The first rate parameters for spiro-cyclisations of O-centred radicals onto aromatics were obtained by the steady-state kinetic EPR method. Pentafluoro-substitution of the ring substantially reduced the spiro-cyclisation rate. Activation barriers of the spiro-cyclisations were computed by DFT to be about half those of the alternative ortho-cyclisations. Consideration of the TS structures suggested the preference for spiro- over ortho-cyclisation resulted from better overlap of the oxyl SOMO with the aromatic π-system during spiro closure.