The invention discloses a method for directly synthesizing alpha-acyloxy ketone derivative containing unsaturated alkene from alpha, beta unsaturated carboxylic acid and a propiophenone compound. The method comprises the step of performing one-pot reaction on alpha, beta unsaturated carboxylic acid, the propiophenone compound and organic hyperoxide under an air environment in a copper compound/tetraalkyl ammonium salt catalytic system to synthesize the alpha-acyloxy ketone derivative. According to the method, the alpha-acyloxy ketone derivative is directly synthesized from the alpha, beta unsaturated carboxylic acid and the propiophenone compound for the first time. The method has the characteristics of high selectivity, high yield, mild reaction condition and simple step and is beneficial to industrial production.