Despite　incorporation　of　organic　groups　into　silica-based　aerogels　to　enhance　their　mechanical　flexibility,　the　wide　temperature　reliability　of　the　modified　silicone　aerogel　is　inevitably　degraded.　Therefore,　facile　synthesis　of　soft　silicone　aerogels　with　wide-temperature　stability　remains　challenging.　Herein,　novel　silicone　aerogels　containing　a　high　content　of　Si are　reported　by　using　polydimethylvinylsiloxane　(PDMVS),　a　hydrosilylation　adduct　with　water-repellent　groups,　as　a　＇flexible　chain　segment＇　embedded　within　the　aerogel　network.　The　poly(2-dimethoxymethylsilyl)ethylmethylvinylsiloxane　(PDEMSEMVS)　aerogel is　fabricated　through　a　cost-effective　ambient　temperature/pressure　drying　process.　The　optimized aerogel　exhibits　exceptional　performance,　such　as　ultra-low　density　(50 mg　cm−3),　wide-temperature　mechanical　flexibility,　and　super-hydrophobicity,　in　comparison　to　the　previous　polysiloxane　aerogels.　A　significant　reduction　in　the　density　of　these　aerogels　is　achieved　while　maintaining　a　high　crosslinking　density　by　synthesizing　gel　networks　with　well-defined　macromolecules　through　hydrolytic　polycondensation　crosslinking　of　PDEMSEMVS.　Notably,　the　pore/nanoparticle　size　of　aerogels　can　be　fine-tuned　by　optimizing　the　gel　solvent　type.　The　as-prepared　silicone　aerogels　demonstrate　selective　absorption,　efficient　oil–water　separation,　and　excellent　thermal　insulation　properties,　showing　promising　applications　in　oil/water　separation　and　thermal　protection.　©　2023　Wiley-VCH　GmbH.