To establish their potential as source of biradicals to initiate free-radical polymerization, 2-methyl- and 2,2,12-trimethylcyclododecanones were photolyzed in the presence of styrene. The initiation efficiency of both ketones is low-0.03. The molecular weight of the obtained polymer is ca. 25% higher than that obtained employing photoinitiators that produce monoradicals. This difference is explained in terms of a mixed polymerization mechanism comprising mono- and biradicals.