Phenols are important readily available synthetic building blocks and starting materials for organic synthetic transformations, which are widely found in agrochemicals, pharmaceuticals, and functional materials. The C–H functionalization of free phenols has proven to be an extremely useful tool in organic synthesis, which provides efficient increases in phenol molecular complexity. Therefore, approaches to functionalizing existing C–H bonds of free phenols have continuously attracted the attention of organic chemists. In this review, we summarize the current knowledge and recent advances in ortho-, meta-, and para-selective C–H functionalization of free phenols in the last five years.