The invention discloses a novel method for synthesizing 4-bromo-1,2-dihydrocyclobuteneo[alpha]naphthalene. The method comprises the following steps: (1) adding 1,2-dihydrocyclobuteneo[alpha]naphthalene, glacial acetic acid and methanol into a low-temperature reactor, stirring, and reducing the temperature to be 10 DEG C below zero to 0 DEG C; (2) dissolving bromine in glacial acetic acid at the temperature of 10 DEG C below zero to 0 DEG C, dripping reaction liquid, preserving the temperature after the dripping operation of the reaction liquid is finished, keeping the reaction liquid in dark place, putting the reaction liquid in a low-temperature cabinet freezer, reacting at the temperature of 30 DEG C below zero to 15 DEG C below zero, and standing the reaction liquid at room temperature; (3) adding the reaction liquid into dichloromethane, extracting an organic phase, adding an aqueous solution of sodium metabisulfite into the organic phase, stirring, standing, layering, washing by using deionized water, separating out the organic phase, and drying; and (4) concentrating the dried organic phase into thick solid, and recrystallizing, thereby obtaining 4-bromo-1,2-dihydrocyclobuteneo[alpha]naphthalene. According to the method disclosed by the invention, 1,2-dihydrocyclobuteneo[alpha]naphthalene synthesized by self research and development serves as a raw material, and 4-bromo-1,2-dihydrocyclobuteneo[alpha]naphthalene with excellent performance and low price is synthesized. The reaction conditions are mild, the operation is simple, and the yield is high.