A novel and simple process for the preparative extraction, separation, and purification of high-purity (-)-borneol and xanthoxylin, synchronously, from the leaves of Blumea balsamifera (L.) DC was developed. Simultaneous distillation and extraction, silica gel column chromatography, and recrystallization were applied to the preparation. Two objective compounds with the purity of 98% were obtained, and the losses were minimal during the whole procedure. It is the first time that the preparation of high-purity (-)-borneol and xanthoxylin at the same time were achieved.