The fluoropolymer–SiO2 hybrid nanocomposite consisting of core–corona fluoropolymer-grafted SiO2 nanoparticle (NP) and poly(dodecafluoroheptyl methacrylate) (PDFHM) was obtained by radical solution polymerization of the vinyl trimethoxy silane (VTMS)-treated SiO2 NP with DFHM in this work. In H2O/tetrahydrofuran (THF) solution, PDFHM self-assembles into dendritic micelle and the increase in H2O volume is favorable for fluoropolymer-grafted SiO2 NPs to create dense fluoropolymer corona layer. It also shows that the addition of H2O to the THF suspension of fluoropolymer–SiO2 nanocomposite could cause a transfer for surface morphology of cast film from smooth film-covered aggregation to bare-exposed flaky aggregation and microsphere aggregation, which results in an increase in surface RMS roughness of cast film and induces a superhydrophobicity. Oleophobicity of cast film can be improved by thermal annealing, because strong surface self-segregation of PDFHM chains during thermal annealing process arouses a marked increase in surface fluorine content.