This thesis details research performed in modeling, simulation, and rational design of porous SOFC cathodes via development, extension, and use of the key tools to aid in the fundamental understanding and engineering design of cathode materials. Phenomenological modeling of triple phase boundary (TPB) reactions and surface transport on La₁₋ₓSrₓMnO₃ (LSM) was conducted, providing insight into the role of the bulk versus surface oxygen reduction pathway and the role of sheet resistance in thin-film patterned electrode measurements. In response to observation of sheet resistance deactivation, a modeling study was conducted to design thin-film patterned electrodes with respect to sheet resistance. Additionally, this thesis outlines the application of phenomenological chemical kinetics to describe and explain the performance and stability enhancements resulting from surface modification of La₁₋ₓSrₓCo₁₋yFeyO₃₋delta (LSCF) with a conformal LSM coating. The analysis was performed in close coordination with electrochemical experiments and transmission electron microscopy. Finally, the thesis describes conformal modeling of porous cathode microstructures using chemical kinetics and transport models. A novel application of conservative point defect ensembles was developed to allow simulations with complicated chemical surface kinetics to be efficiently coupled with bulk transport within the porous structure. The finite element method was employed to simulate electrochemical response conformal to sintered porous ceramic structures using actual 3D microstructural reconstructions obtained using x-ray microtomography. Mesh refinement, linear, and nonlinear reaction rate kinetics were employed to study the bulk versus surface oxygen reduction pathways and the effect of near-TPB nanostructure.