In this study, we adopted rubbing alcohol (2-propanol/water = 7.8/2) as the solvent to prepare hydrophobic poly(methyl methacrylate) (PMMA) nanofibers (with submicron scale diameters) by electrospinning. In the literature, the general solvents, such as acetone, tetrahydrofuran, chloroform, toluene, etc., to dissolve PMMA are harmful and not environmentally friendly. 2-Propanol and water are both not hazardous to humans and the environment. PMMA dissolved in rubbing alcohol can be electrospun near room temperature. The solutions were heated at ~60 °C and allowed to cool to room temperature. Controlling the solution concentration and electrospinning parameters, fibers with diameters of 0.65~0.85 μm were obtained. The electrospun PMMA mats were hydrophobic with contact angles > 130 ° and showed good water resistance.