Poly(vinylidene fluoride) (PVDF) has reached the second largest production volume of fluoropolymers in recent years, and its popularity can be ascribed to high thermal stability and chemical inertness combined with its ferroelectric behavior. Copolymerization of vinylidene fluoride with other monomers leads to a wide variety of products with modified or improved properties. Besides commercially available fluorinated random copolymers, well-defined block-, graft, and alternating copolymers based on PVDF received more attention in recent years. PVDF-containing block copolymers that may self-assemble into well-ordered morphologies are of particular interest, being potential precursors for functional nanostructured materials applicable in membranes and electronics. This Highlight provides an overview of the routes developed towards these materials via conventional and controlled polymerization techniques. In addition, it discusses their nano-scopic phase behavior and current and potential applications. (C) 2014 Wiley Periodicals, Inc.