Brown rice, an important material of whole-grain food, is increasingly popular for its health benefits. Thus, seven varieties of brown rice from southern China were analyzed in this study, concerning the free and bound phenolic compounds in the extract. The phenolic profiles of different brown rice were obtained and compared by the combination of HPLC and LC-MS analysis, in which eleven phenolic acids were identified. It was indicated that the total phenolic contents of different brown rice varied from 92.32 to 196.54 mg of gallic acid equivalent (GAE)/100 g DW. Ferulic acid and p-coumaric acid, free and bound, dominated within the phenolic acids. To be mentioned, the total phenols of Luotiangongmi (a kind of red rice) were significantly higher than the other six varieties. The high phenolic content of brown rice can further guide us to explore the functional properties of the crops.