An agomelatine hydrobromide hydrate of formula (I), in which X is Br, preparation method and use thereof as well as pharmaceutical composition containing it are provided. The solubility of the agomelatine hydrobromide hydrate obtained by the present method is significantly higher than that of agomelatine. Therefore, it is more suitable for manufacturing pharmaceutical formulations. In addition, the product has higher stability and purity. The present product of high purity can be obtained through a simple process, rather than process with complicated steps.