The invention discloses a method for synthesizing optically pure 2-hydroxymethyl-1,4-benzodioxin and derivatives of the optically pure 2-hydroxymethyl-1,4-benzodioxin. The method comprises the steps that cheap 2-bromophenol or derivatives of the 2-bromophenol and glycidyl butyrate are taken as raw materials, and through C-O bond coupling by means of light/nickel concerted catalysis, the opticallypure 2-hydroxymethyl-1,4-benzodioxin or the derivatives of the optically pure 2-hydroxymethyl-1,4-benzodioxin are obtained. The compound is a key intermediate with important bioactive molecules. The method has the advantages that 1) the dosage of a photocatalyst is low; 2) simple nickel salt is taken as a metal catalyst, and a ligand does not need to be added such as nickel bromide; 3) the reaction condition is mild, and a reaction can be effectively carried out at 60-80 DEG C. The method have the advantages that the process is simple, the reaction condition is mild, the price of the catalystis low, environmental friendliness is achieved, the yield is high, and the method has good industrial application prospects.