Surface of pristine silica aerogel nanoparticles was hydrophobically modified with hexamethyldisilazane (HMDS). Then, the resultant modified nanoparticles were used for in situ atom transfer radical copolymerization of styrene and methyl methacrylate. Surface area and structural characteristics of the HMDS-modified silica aerogel nanoparticles (H-SANs) were examined by nitrogen adsorption/desorption isotherm. Evaluation of size distribution and morphological studies were also performed by scanning electron microscopy and transmission electron microscopy. Conversion and molecular weight determinations were carried out using gas chromatography and size exclusion chromatography, respectively. Adding of H-SAN by 3 wt% results in decrement of conversion from 98% to 79%. In addition, molecular weight of copolymer chains decreases from 20,372 g·mol−1 to 16,487 g·mol−1. However, polydispersity index values increases from 1.38 to 1.76. Linear increase of ln( M 0/ M) with time for all the samples shows that polymerization proceeds in a living manner. Increasing thermal stability of the nanocomposites is demonstrated by thermal gravimetric analysis. Differential scanning calorimetry shows a decrease in glass transition temperature from 67.4°C to 59.8°C by the addition of 3 wt% of the H-SAN.