A Cu(0)/Selectfluor system-mediated oxidative cyclization of 1,5-enynes with concomitant C鈥揅 bond cleavage to access 3-formyl-1-indenone derivatives is described. Preliminary mechanistic investigations disclosed that the C鈥揅 bond cleavage involved a novel water-participated oxygen-insertion 尾-carbon elimination through double oxycuprations.