The thermolysis of four alkylperoxy esters was undertaken at various temperatures between 300 and 353 K and the radicals generated were trapped employing DMPO, DEPMPO, PBN-d14 and TTBNB. The adducts of a range of second-generation carbon-centred radicals, formed via decarboxylation of the acyloxyl moiety, including those of the 2,4,4-trimethylpentyl and hept-3-yl radicals, were also observed. The co-generated tert-alkoxyl radicals, released during the thermolysis of tert-butylperoxy-3,3,5-trimethylhexanoate, tert-amylperoxy-2-ethylhexanoate and the bifunctional peroxide 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, were all successfully trapped, as were a range of second-generation carbon-centred radicals formed following -scission of these tert-alkoxyl radicals.