In this work, new insights into impacts of the polytetrafluoroethylene (PTFE) binder on high temperature polymer electrolyte fuel cells (HT-PEFCs) are provided by means of various characterizations and accelerated stress tests. Cathodes with PTFE contents from 0 wt% to 60 wt% were fabricated and compared using electrochemical measurements. The results indicate that the cell with 10 wt% PTFE in the cathode catalyst layer (CCL) shows the best performance due to having the lowest mass transport resistance and cathode protonic resistance. Moreover, cyclic voltammograms show that Pt (100) edge and corner sites are significantly covered by PTFE and phosphate anions when the PTFE content is higher than 25 wt%. Open-circuit and low load-cycling conditions are applied to accelerate degradation processes of the HT-PEFCs. The PTFE binder shows a network structure in the pores of the catalyst layer, which reduces phosphoric acid leaching during the aging tests. In addition, the high binder HT-PEFCs more easily suffer from a mass transport problem, leading to more severe performance degradation.