The goal of this work is to study electrical transport within multiphase structures of Li-ion electrodes through numerical microstructure reconstruction and direct evaluation. Li-ion battery electrodes at different compositions were numerically reconstructed mimicking the experimental fabrication process. Electrode material agglomeration and interfaces between components, as well as possible implication on battery performance were explored. Distribution of electrode phases (active material particles, binder, conducting phase carbon), and electrical conductivity were studied upon the reconstructed 3D microstructure. The electrical conductivity of the electrodes was estimated from the reconstructed electrode structures, and compared favorably with those measured experimentally using four-probe tests. It has been found that macro mass transport properties of the numerically reconstructed electrodes depend critically on nanoscale physical characteristics of electrode components and their contact. This work revealed the localized nanoscale electrode complexity and transport processes in great details, which are currently difficult to investigate experimentally or by alternative models. (C) 2012 Elsevier B.V. All rights reserved.