Layered Li-transition metal oxide compounds of the form LiMO₂ serve as chemically stable, energy dense active cathode materials for Li-ion batteries. Among these materials Li(Ni_1/3Mn_1/3Co_1/3)O₂ (NMC) has received increased attention due to its improved rate capability compared to other  LiMO₂ cathode materials. Forging a stronger connection between complex mesoscale electrode geometry, material performance, and processing techniques can enable development of practical approaches for realizing electrode performance controlled by mesoscale geometry. To this end, 3D x-ray imaging, microstructural characterization, and computational modeling techniques have been applied to analyze the charge/discharge behavior of the active material in a set of NMC cathodes subject to varied processing approaches. For the present studies, the cathodes were produced using combinations of rapid or gradual drying process along with ball milling and calendaring prior to cutting into coin cell electrodes. Samples were extracted from pristine cathodes and imaged using x-ray nanotomography approximately halfway between the Co and Ni K-absorption edges. Imaging at this x-ray energy provided clear contrast between the NMC phase and the carbon/binder/pore regions within the samples. Particle geometry was characterized and compared for samples from four cathodes treated with distinct combinations of preparation steps. Geometric characteristics of the active cathode material include the particle size distribution, surface area, volume, and sphericity. Following characterization the tomographic data sets were applied as computational domains in multiphysics transport models to assess the effects of processing methodology on charge/discharge performance. Distinct variation in particle count and geometry is observed within the samples analyzed. The performance implications of this variation are discussed, particularly with respect to charge/discharge capabilities. A comparison is also made for particles with varied degrees of mechanical degradation.