Resorcinol‐formaldehyde based carbon aerogel has been tailored to meet the requirements as a Fe‑N‑C carbon support, aiming to provide sufficient, inexpensive cathode catalyst for high‐temperature polymer electrolyte membrane fuel cells (HT‑PEMFCs). Therefore, different treatments of the aerogel are explored for optimal pore structure and incorporation of surface functionalities, which are crucial for Fe‑N‑C synthesis and electrochemical performance. Fe‑N‑Cs of differently modified aerogel are investigated in phosphoric acid electrolyte. The results show that HNO3 treatment for 5 h yields the Fe‑N‑C with highest mass activity and selectivity, attributed to the highest amount of nitrogen functionalities revealed by energy dispersive X‐ray spectroscopy (XPS) and proper Fe‑Nx site formation. HNO3 oxidation for 2 h leads to Fe‑N‑C with slightly lower oxygen reduction reaction (ORR) activity and selectivity. In contrast, the Fe‑N‑C synthesized from CA with H3PO4 treatment shows negligible ORR activity. The feasibility of one‐step activation and carbonization treatment with K2CO3 and, for the first time, with K2CO3 and melamine is proven as the obtained Fe‑N‑Cs exhibit promising ORR activity. The results are compared with the commercial Fe‑N‑C PMF‐014401. This study contributes to the advancement of cost‐efficient HT‑PEMFCs by optimizing Fe‑N‑C catalyst properties.