The catalytic oxygen reduction reaction (ORR) at the cathode is a critical process to proton exchange membrane fuel cell (PEMFC) operation. The current catalyst materials of choice are platinum group metals (PGMs) with high costs and limited reserves. Reported herein are our recent efforts in developing non-PGM electrocatalyst materials using rational design and synthesis. A variety of porous organic materials were developed as the catalyst precursors for preparing of ORR catalysts with high surface area and active site density free of carbon support. Electrocatalytic activities and physical properties of the new catalysts were investigated by various techniques in the process of understanding of the active site formation.