The rational design of highly efficient, low-cost, and durable electrocatalysts to replace platinum-based electrodes for oxygen reduction reaction (ORR) is highly desirable. Although atomically dispersed supported metal catalysts often exhibit excellent catalytic performance with maximized atom efficiency, the fabrication of single-atom catalysts remains a great challenge because of their easy aggregation. Herein, a simple ionothermal method was developed to fabricate atomically dispersed Fe–Nx species on porous porphyrinic triazine-based frameworks (FeSAs/PTF) with high Fe loading up to 8.3 wt %, resulting in highly reactive and stable single-atom ORR catalysts for the first time. Owing to the high density of single-atom Fe–N4 active sites, highly hierarchical porosity, and good conductivity, the as-prepared catalyst FeSAs/PTF-600 exhibited highly efficient activity, methanol tolerance, and superstability for oxygen reduction reaction (ORR) under both alkaline and acidic conditions. This work will bring new inspiration to the design of highly efficient noble-metal-free catalysts at the atomic scale for energy conversion.