Benzoic acid residue is solid waste produced from the production of benzoic acid by oxidizing toluene. Because it contained important chemical raw materials such as benzoic acid, benzyl benzoate and fluorenone, it is necessary to recover them from the residue. In this work the technique featured with high efficiency evaporation and vacuum distillation was developed to obtain total recovery and utilization of the benzoic acid residue. By controlling the operation temperature at 260 degrees C and the pressure of 16 kPa in the rising and falling film evaporators, heavy components separated efficiently from the residue can be polymerized and the light components consisting of 63% of the residue entered into a benzoic acid vacuum distillation column. Keeping the temperature of polymerization at (280 +/- 10)degrees C, coumarone resin was produced after adjusting the softening point according to the market requirements. Vacuum distillation was operated under the following conditions: top temperature at 186 degrees C, top pressure of 16 kPa, bottom temperature at 240-250 degrees C, reflux ratio being 3 : 1. Benzoic acid of 98% purity was distilled out from the column as a side stream and the bottom product was crude benzyl benzoate. By the developed technique, the benzoic acid residue was splitted into three products, benzoic acid, crude benzyl benzoate and coumarone resin without any surplus waste.