This research investigated the influence of binary solutions of benzene and methanol for their vapor flammability characteristics. The different mixing ratios (100/0, 75/25, 50/50, 25/75 and 0/100 vol%) samples were injected into a 20-liter spherical explosion vessel under various initial temperatures (100, 150 and 200C) to study their flammability behaviors. According to the experimental results, the flammability diagram of mixtures can be completely illustrated and combined with specific safety-related properties such as lower explosion limit (LEL), upper explosion limit (UEL), minimum oxygen concentration (MOC), maximum explosion overpressure (Pmax), and gas or vapor deflagration index (Kg). The experimental results showed that the UEL, Pmax and Kg all increased with the temperature, pressure and oxygen concentration, whereas there was no significant variation on the part of LEL. The results can provide specific information on fire and explosion hazards for related industries.