A Monte Carlo percolation model has been developed and utilized to characterize the factors controlling triple phase boundary (TPB) formation in an SOFC electrode. The model accounts for (1) electronic conductor, ionic conductor, and gas phase percolation, (2) competition between percolation of gas and electronically conducting phases, and (3) determination of continuous, though not necessarily fully percolating, paths from TPBs to the bulk phases. The model results show that physical processes near the TPB, such as sorbate transport, significantly affect TPB formation in a composite electrode. Active TPB formation is found to be most significantly dependent upon continuous and competing percolation of multiple phases. Simultaneously requiring continuous paths and accounting for non-continuous boundary conditions results in lower active TPB formation levels (up to 8% of possible sites) than presented in the literature (75% of possible sites). In addition, the varying ratio of active to potential TPB sites predicted by the current model (up to 80%) differs significantly from the constant reported in the literature (80%), which lacks analyses of three-phase percolation, gas phase paths, and gas/current collector boundary conditions. This dependence of active TPB formation on percolation of all three phases is important to understand as a basis for determining SOFC performance and optimization. (c) 2007 Elsevier Ltd. All rights reserved.