Despite their unique properties, pure silica aerogels usually exhibit a few applications on a large-scale due to their hydrophilic behavior and brittleness. To overcome these drawbacks, hydrophobic, fiber-reinforced tetraethoxysilane/vinyltrimethoxysilane (TEOS/VTMS) derived aerogels were synthesized and dried at ambient pressure and under supercritical conditions for comparison. The silylation of the silica surface is crucial prior to ambient pressure drying (APD) and is favored by the already existing vinyl groups in the silica skeleton. In this work, the influence of different silylating agents on the final properties of the aerogels was studied, varying the number of methyl groups of the agent. With the increase of methyl groups in the agent and/or its reactivity, the decrease of shrinkage by APD is more pronounced, reaching values similar to the supercritically dried counterparts. The thermal insulation performance, hydrophobicity and flexibility improve in the same trend.