For production of biodiesel from bio oils by heterogeneous catalysis, high performance catalysts of transesterification and the further utilization of glycerol have been the two points of research. The process seemed easy, however, has never been well established. Here we report a novel design of catalytic distillation using hierachically integrated CNTs-based holistic catalyst to figure out the two points in one process, which shows high performance both for the conversion of bio oils to biodiesel and, unexpectedly, for the conversion of glycerol to more valuable chemicals at the same time. The method, with integration of nano, meso to macro reactor, has overwhelming advantages over common technologies using liquid acids or bases to catalyze the reactions, which suffer from the high cost of separation and unsolved utilization of glycerol.