This feature article highlights three types of hyperbranched fluoropolymers (HBFPs) with different structural features, which were synthesized by either polycondensation of fluorinated AB(chi) monomers or self-condensing vinyl (co)polymerization of fluorinated inimers and/or fluorinated comonomers. Amphiphilic crosslinked networks with hybridization of these hydrophobic HBFPs and linear hydrophilic poly(ethylene glycol)s are also discussed. As microphase-segregated materials with nanoscale surface heterogeneities, these networks possessed unusual anti-biofouling abilities, atypical sequestration and release behaviors for guest molecules, and special mechanical properties.