Methanol is a potential and oxygenated, clean, renewable liquid fuel in the near future. Compared with hydrogen, methanol is more practical, safe, and convenient for storage, transportation, and distribution. For the concept of the methanol economy, it can be regarded as an energy carrier for all traditional and alternative energy sources. It can be prepared from syngas, which is a mixture of hydrogen and carbon monoxide obtained not only from fossil fuel but also biomass gasification. It also can be produced by recycling carbon dioxide. For liquid fuel, spray combustion is an energetic method for combustion. For furnace applications, spray combustion is of considerable technological significance to a diversity of applications ranging from furnaces, boiler, IC engine, domestic heating, and even to space rockets. In the present study, the flame stabilization and the effect of flow rate were observed and characterized. The emissions in terms of emission index of CO (EICO) and emission index of NOx (EINOx) were measured for comparison with fossil fuel spray combustion. In addition, the effect of water content in methanol on flame stabilization, emissions, and relative efficiency are also evaluated. The result shows that as the water content in the fuel mixture is greater than 10%, the flames cannot be sustained. The appearance of the flames was not significantly different for various water contents in the fuel mixture. However, the flame length was reduced by the increase of water contents, but there was no apparent change in the flame lift-off height. Due to the lower flame temperature, the nitrogen oxide emission is reduced. Conversely, carbon monoxide emission is increased, and the conversion rate of the combustion is also decreased. As the water content in the fuel mixtures increases by 10%, the exergy efficiency reasonably decreases by 9.98%, but the thermal efficiency reduces by 26.61%. It is interesting to note that the effect of water contents in the fuel mixture on the exergy destruction is minor. This research provides several important conclusions related to the methanol spray combustion in an open space. Understanding the spray combustion of methanol and its stabilization, emissions, and relative efficiency will be useful to serve as the basis for further high-efficiency application and control of the flame and combustion for methanol.