Membrane distillation (MD) and membrane electrolysis (ME) were evaluated for simultaneous fresh water extraction and NaOH production from a mixture of NaCl and NaHCO3 to simulate the composition of coal seam gas (CSG) reverse osmosis (RO) brine. Experimental results demonstrate the potential of MD for producing fresh water and simultaneously concentrating CSG RO brine prior to the ME process. MD water flux was slightly reduced by the increased feed salinity and the decomposition of bicarbonate to CO2 during the concentration of CSG RO brine. MD operation of CSG RO brine at a concentration factor of 10 (90% water recovery) was achieved with distillate conductivity as low as 18 μS/cm, and without any observable membrane scaling. Exceeding the concentration factor of 10 could lead to deterioration in both water flux and distillate quality due to the precipitation of NaCl, NaHCO3, and Na2CO3 on the membrane. With respect to ME, current density and water circulation rates exerted strong influences on the ME process performance. Combining ME with MD reduced the thermal energy requirement of ME by 3 MJ per kg of NaOH produced and the thermal energy consumption of MD by 22 MJ per m3 of clean water extracted.