Calorific value of mixed gas, like liquefied natural gas (LNG), is strongly depends on its compositions which are affected by the mining place and producing time. The variation in calorific value have an direct influence on the combustion characteristics and performances of boiler, burner, vehicle, power plants etc. Thus, developing experimental method to measure exact calorific value is becoming an issue in the related industrial fields. Flame calorimeter is developed to get calorific value at the dynamic equilibrium state using electric substitution method. Refrigerant-11 carries heat from combustor and/or heater to the Peltier elements which pumped it out to the cooling water. It is found out that error in the measured calorific value of methane is 2.86% compared with the theoretical one. Developed design technique and the experimental data will be applied to design the national standard gas calorific value measuring apparatus.