Surface modification, which is simply about the end-capping of the reactive silanol groups located in silica wet gel to satisfy hydrophobic behavior, has great importance in the production of silica aerogels in ambient conditions. In this study, silica aerogels were synthesized with a sol-gel method via ambient pressure drying. A two-step surface modification was performed on wet gels by using various silanes with different contents (6%, 10% or 20% by vol in n-hexane) to control the extent of irreversible shrinkage during drying. Mono-functional (TMCS) and three-functional silanes (MTMS, MTES and MEMO) were selected for this purpose. The impact of the type and amount of the silylating agents on the microstructure, pore characteristics and hygroscopic nature of resulting aerogels were identified by conducting FTIR, SEM and BET analyses and contact angle measurements. According to characterization results, MTES exhibits a competitive performance compared to classically used TMCS, as the silica aerogels modified with 10% of MTES was obtained in a well-developed with mesoporous structure with very high specific surface area (SBET = 964m2/g) and high hydrophobicity (Θ = 137°). On the other hand, organically functionalized silane MEMO and MTMS, also display noteworthy results (monolithical structure with highly developed porous network and high degree of hydrophobicity) at the low contents (at 6% and 10%). These outcomes are crucial as they may encourage the future attempts on introducing three-functional silanes during surface modification, as these silanes yield high silylation performance and causes the synthesis of well-qualified silica aerogel in ambient conditions.