A novel layer-upon-layer bipolar electrode system (nLBPEs) possessing the ability of increasing spacetime yields was developed for efficient treatment of industrial wastewaters. The cellulose acetate coated granular activated carbon (CA-GAC) was used as insulating layer to avoid short circuit current, which could effectively enhance the electro-oxidation. In addition, the excellent performances of the nLBPEs are theoretically described by introducing the fraction of current applied to particulate electrode, tfr, which relies on the characteristics of carbon particles, organic matters (OMs) and solutions. The kinetics could provide proper preparation and selection of the filings in accordance with the characteristics of OM. Moreover, the presented nLBPEs is superior to the conventional three dimension electrode and shows broad interests and perfect performances in different kinds of industrial wastewater treatment. (C) 2012 Elsevier B.V. All rights reserved.