In this study, two systems are brought forward to recover the waste heat of a proton exchange membrane fuel cell (PEMFC), which are named the organic Rankine cycle (ORC), and heat pump (HP) combined organic Rankine cycle (HPORC). The performances of both systems are simulated on the platform of MATLAB with R123, R245fa, R134a, water, and ethanol being selected as the working fluid, respectively. The results show that, for PEMFC where operating temperature is constantly kept at 60 °C, there exists an optimum working temperature for each fluid in ORC and HPORC. In ORC, the maximal net power can be achieved with R245fa being selected as the working fluid. The corresponding thermal efficiency of the recovery system is 4.03%. In HPORC, the maximal net power can be achieved with water being selected in HP and R123 in ORC. The thermal efficiency of the recovery system increases to 4.73%. Moreover, the possibility of using ORC as the cooling system of PEMFC is also studied. The heat released from PEMFC stack is assumed to be wholly recovered by the ORC or HPORC system. The results indicate that the HPORC system is much more feasible for the cooling system of a PEMFC stack, since the heat recovery ability can be promoted due to the presence of HP.