Co-sensitized photooxygenation of 1,1-diphenyl-2-vinylcyclopropane (VCP-DPh) with 9,10-dicyanoanthracene and biphenyl in oxygen-saturated acetonitrile solution produced 3,3-diphenyl-5-vinyl-1,2-dioxolane as the major product. The same photoproduct was obtained by acetone sensitized photooxygenation in oxygen-saturated acetone solution. However, VCP-DPh remained intact when directly irradiated with DCA or irradiated with Rose Bengal to generate singlet oxygen. A mechanism involving a cosensitizer radical cation and sensitizer radical anion is proposed.