In this work, we describe the successful synthesis of super-hydrophobic polymethylsilsesquioxane (PMSQ) aerogels with a porous network by a sol-gel polymerization process using methyltrimethoxysilane (MTMS) reactants with the addition of cetyltrimethylammonium bromide (CTAB) surfactants. The specific surface area, pore size and hydrophobicity of the CTAB-modified PMSQ aerogels were investigated for different amounts of CTAB doping. The specific surface areas of the pristine and CTAB-modified PMSQ aerogels with C/M molar ratios of 0.001, 0.002 and 0.004 were 491, 301, 342 and 298 m²/g, respectively. The water contact angles of the CTAB-modified PMSQ aerogels with C/M molar ratios of 0.001, 0.002 and 0.004 were 166.38°, 165.62° and 166.43°, confirming the super-hydrophobicity of the CTAB-modified PMSQ aerogels. Compared to pristine PMSQ aerogels, the as-prepared CTAB-modified PMSQ aerogels exhibit more solvent-resistant properties in ethanol (EtOH) and n-hexane solvents. The as-prepared CTAB-modified PMSQ aerogels were further used for organic solvent and oil adsorption applications. Consequently, the as-prepared CTAB-modified PMSQ aerogels have great potential for organic solvent and oil adsorption in industrial applications.