Herein, an approach is proposed to analyze the tortuosity of porous electrodes using the radical Voronoi tessellation. For this purpose, a series of particle compacts geometrically similar to the actual porous electrode were generated using discrete element method; the radical Voronoi tessellation was constructed for each compact to characterize the structural properties; the tortuosity of compact porous structure was simulated by applying the Dijkstra’s shortest path algorithm on radical Voronoi tessellation. Finally, the relationships were established between the tortuosity and the composition of the ternary particle mixture, and between the tortuosity and the radical Voronoi cell parameters. The following correlations between tortuosity values and radical Voronoi cell parameters were found: larger faces and longer edges of radical Voronoi cell leads to the increased fraction of larger values of tortuosity in the distribution, while smaller faces and shorter edges of radical Voronoi cell contribute to the increased fraction of smaller tortuosity values, being the tortuosity values more uniform with narrower distribution. Thus, the compacts with enhanced diffusion properties are expected to be obtained by packing particle mixtures with high volume fraction of small and medium particles. These results will help to design the well-packed particle compacts having improved diffusion properties for various applications including porous electrodes.