Photolysis of azoazoxyalkane 9 and thermolysis of beta-azoxyperester 13 afford beta-azoxy radicals 1 and 14, respectively. One reaction pathway of these radicals is cyclization to azoxy oxygen to form cyclic hydrazyl radicals 2 and 16 that fragment to a ketone or aldehyde plus hydrazonyl radical 3. The analogous hydrazyl radical 6 need not be invoked in the case of gamma-azoxy radical 5, which instead undergoes a rare solution phase beta-scission to lose ethylene. Surprisingly, the same beta-scission was found in the 3,3-dimethyl-4-pentenyl radical (34), a hydrocarbon analogue of 5.