The mass transfer and related electrochemical reactions in the catalytic layer (CL) are crucial for the performance of high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs), but there is a lack of understanding of the optimal phosphoric acid content and Pt/C catalyst loading in the CL. In this work, we investigate the influences of Pt/C catalyst numbers (NPt/C) and phosphoric acid film thickness (δPA) on mass transfer and electrochemical reactions of the cathode CL using a pore-scale model (300 × 300 × 300 nm3). The results reveal that larger NPt/C and δPA can impede oxygen diffusion, while lower NPt/C and δPA lead to fewer reaction active sites and lower conductivity, both of which result in lower current density. Therefore, the balance of three-phase transport is extremely important for CL. There is a 3D volcanic relationship between current density, Pt/C catalysts, and phosphoric acid film. At NPt/C = 200 (7407 per μm3) and δPA = 4 nm (the volume fractions of 37.22 % and 17.87 %), the highest current density can be achieved at a potential of 0.5 V (vs. RHE), which increased with the decrease of potential. This work is valuable for understanding the optimizing the microstructure and three-phase transport pathway of the CL to improve the performance of HT-PEMFCs.