The invention belongs to the field of electrochemical organic synthesis, and particularly relates to a device and method for device and method for coupled electro-catalytic hydrogen peroxide production and selective organic matter oxidation. According to the invention, the reaction device is composed of an anode chamber, a cathode chamber and an organic catalysis chamber, wherein the cathode chamber contains a catalyst for hydrogen peroxide production through oxygen reduction; the anode chamber contains a water oxidation or hydrogen oxidation catalyst; the organic catalysis chamber contains an organic matter oxidation catalyst; the anode chamber and the organic catalysis chamber are separated by a cation exchange membrane; and the cathode chamber and the organic catalysis chamber are separated by an anion exchange membrane. During working of the device, oxygen or air is introduced into the cathode chamber, hydrogen or water is introduced into the anode chamber, and an organic reactant is introduced into the organic catalysis chamber; and under an electrifying condition, a cathode is subjected to oxygen reduction to obtain OOH<->, an anode is subjected to water oxidation or hydroxide reaction to obtain H< + >, the H<+> enters the middle organic catalysis chamber through the corresponding anion and cation exchange membranes to form H2O2, and organic matters are further oxidized under the action of the catalyst. According to the invention, low-concentration hydrogen peroxide generated by oxygen reduction is directly used for oxidation of the organic matters, so problems in separation, concentration, storage and transportation cost and safety of H2O2 are avoided, and remarkable economic benefits are achieved. When the device is used for phenol oxidation, benzyl alcohol oxidation, furfuryl alcohol oxidation and cyclohexanone conversion, the selectivity of target products including benzenediol, benzaldehyde, furfural and cyclohexanone-oxime is greater than 98%, and corresponding total current efficiency is 21-49%.