A hydrophobic porous silica aerogel composite membrane for a vacuum membrane distillation device and a vacuum distillation method are disclosed. The vacuum membrane distillation device has a case and the hydrophobic porous silica aerogel composite membrane accommodated in the case to divide a chamber defined by the case into a feed part configured to feed a first fluid containing water molecules and a permeate part configured to collect a second fluid containing the water molecules. The hydrophobic porous silica aerogel composite membrane includes a porous aluminum oxide membrane that has a plurality of first pores with average pore diameter larger than 50 nm and a porous silica aerogel membrane that has a plurality of second pores of 2 to 50 nm and is formed on at least one side of the porous aluminum oxide membrane facing the feed part by methylmethoxysilane as a precursor and a sol-gel synthetic process.