The invention discloses a process for synthesizing p-bromophenol. The process comprises the following steps of adding a certain amount of phenol and chloroform which serves as a solvent into a four-mouthed flask which is equipped with a stirrer, a thermometer, a dropping funnel and a gas absorption device, and uniformly mixing; starting up the stirrer to start stirring, inserting the thermometer and the dropping funnel into the four-mouthed flask, completely dissolving phenol in chloroform, then controlling the external temperature of the flask to be -5 DEG C or less, starting to dropwise add bromine through the dropping funnel, controlling the dropwise adding speed so as to maintain the internal reaction temperature of the flask to be 9 DEG C or less, and carrying out stirring reaction for a period of time after the dropwise adding process is ended; heating to the temperature of 12-23 DEG C after the reaction is ended, introducing nitrogen gas to completely expel hydrogen bromide gas in the four-mouthed flask, cooling to the temperature of about 6 DEG C, putting 0.14-0.22 g of p-bromophenol crystal with the purity of higher than 99.1% into the four-mouthed flask, taking the p-bromophenol crystal as a seed crystal, starting to precipitate a crude product, stirring for 22 minutes, discharging, and carrying out depressurized suction filtration by using a Buchner funnel; and washing the crude product with chloroform, then drying, and thus obtaining the p-bromophenol product. The process has the advantages of simplicity, fewer steps, easy operation, low cost, and high product quality.