The phase behavior of W/O microemulsion employed blend NPE4.2 and NPE10 as surfactants was studied. The influence of blend surfactant proportion, surfactant dose co-surfactant dose, various cations and temperature on W/O microemulsion phase behavior was examined by way of electric conductivity with the maximum dissolve water (solution) being the target. Experiments indicated that as the NPE 4.2 :NPE 10 is about 1.2:1 and (S+A):O is about 3:7, the maximum dissolve water was acquired. When the water was substituted by other cations solution or the temperature was increased, the effect to the microemulsion was resemble to the water. But the domain of W/O microemulsion is decreased.