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In this paper two micro-nano iron oxide materials were prepared，these particles ar-e uniform flowerlike in shape and size with a diameter around 1.0～1.5μm，the pet-als of the flower are composed of interconnected nano crystals about 15nm in diame-ter. The materials prepared were applied in the degradation of HCB.The destructionof HCB by material with multiphase of α-Fe2O3 and Fe3O4 was faster than that of pu-re phase of α-Fe2O3. Time dependent reaction was carried out to study furtherly t-hemechanism of reaction of HCB and α-Fe2O3 and Fe3O4 multiphase material.The amou-nt ofdetected CBs intermediate products can reach 65％. So，that dechlorination/hyd-rogenation is the main degradation pathway of HCB on this multiphase micro-nano ma-terial can be deduced well-foundedly. Basically the amountof 1,2,3,4-TeCB，1,2,3,5-TeCB an-d 1,2,4,5-TeCB were at the same level，1,2,4-TrCBand 1,2-DCB were the main dechlorination products comparing with their otherisomers. And the step from TeCB to TrCB was the slowest in the dechlorinationreaction of HCB，so it was supposed th-at the dechlorination speed of HCB mightdependent on this step. PCBs and another s-eries of chlorine contained substanceswere detected in the destruction products. T-hey both dechlorinated together with theCBs. The dechlorination pathways of HCB bythe multiphase micro-nano materialwere proposed in this study. More over，the proposal manner in this study is muchsuitable for the treatment of HCB in storage. HCB i-s isolated in an obturator，treatedin a much lower temperature than incineration t-echnology. In this process，workerstake no exposure risk. And lower chlorinated be-nzenes are the main products，whichmight be collected for industry or pharmaceut-ical usage. The present resultspromisingly take an important role in the elimina-ting of persistent organic pollutants.