A method of decomposing a phenol by-product produced in a phenol preparation process, in which acetophenone separated from a distillation column is mixed with tar separated and collected in a decomposition reactor, thereby significantly decreasing viscosity of tar. The decomposition method according to the present invention allows tar to have sufficient viscosity for flowability even at room temperature, whereby transfer and storage of tar may be more smoothly done without using any heating device for transfer of tar.