For obtaining the data that contributes to propose detailed chemical reaction mechanism including the evaporation process of the liquid fuel, experimental study of counterflow pool combustion was conducted. The double flame that is known as a feature of Monomethylhydrazine (MMH)/Nitrogen Tetroxide (NTO) non-premixed flame was formed in this experiment. With respect to the counterflow pool combustion of MMH/NTO in this study, we carried out the high speed shooting and chemiluminescence measurement. The results obtained by the experiments were compared with the numerical simulation with OPPDIF/CHEMKIN-Pro. Results showed good agreement with experimental results in combustion area.