Toluene is used for various purposes such as a cleansing agent, paint thinner, lacquers, printing, and leather tanning process. However, it has an adverse effect on human bodies, such as skin irritation, leukemia, respiratory issues, mutagenicity, etc, when the chemical gets mixed in drinking and rainwater by the above routes. Therefore, there is a threat to the environment and society because of the presence of toluene in water bodies through industrial effluent. Henceforth, in this study, toluene is separated from water using the air gap membrane distillation (AGMD) process. The hydrophobic microporous poly-tetra- fluoro-ethylene has been employed for this purpose. Primarily, this work focussed on the study of operating parameters such as feed solution temperature and coolant temperature on the AGMD performance namely permeate flux and toluene selectivity. It was observed that the permeate flux increased exponentially from 2.07 kg/m2h to 9.23 kg/m2h, and 0.94 kg/m2h to 3.53 kg/m2h. However, it was found that the permeate flux decreased from 9.48 kg/m2h to 8.12 kg/m2h, and 3.78 kg/m2h to 2.42 kg/m2h on increasing the coolant temperature from 5°C to 25°C at 3 mm and 11 mm air gap, respectively. The membrane selectivity was found to be less than 1, which signifies the efficient toluene-water separation. In order to study the membrane performance in the long run, the permeate flux was estimated continuously till 60 h wherein the estimated flux was found to be almost constant. The membrane morphology before and after the 60 h experimental run was analysed using capture FE-SEM micrographs. The toluene concentration was estimated using a spectrophotometer at a wavelength of 264 nm.