The invention discloses a method for directly synthesizing unsaturated-olefin-containing alpha-acyloxyketone derivatives from alpha,beta unsaturated carboxylic acids and ketone compounds. The method comprises the following step: in an air environment, carrying out one-pot reaction on alpha,beta unsaturated carboxylic acids, ketone compounds and organic peroxides in a copper compound/tetraalkyl quaternary ammonium salt catalytic system to synthesize the unsaturated-olefin-containing alpha-acyloxyketone derivatives. According to the method, the unsaturated-olefin-containing alpha-acyloxyketone derivatives are directly synthesized from the alpha,beta unsaturated carboxylic acids and ketone compounds for the first time; and thus, the method has the characteristics of high selectivity, high yield, mild reaction conditions, simple steps and the like, and is beneficial to industrial production.