This review highlights the synthesis, properties and applications, as well as the potential, of the rarely appeared in the literature poly(vinylidene fluoride) (PVDF)-based complex macromolecular architectures (CMAs). PVDF, the second in production fluoropolymer, is an attractive material due to its outstanding properties (high thermal stability and chemical inertness) along with its piezo-, pyro-and ferro-electrical performance. So far, although studies on the PVDF-based CMAs are limited, there is a growing interest in the synthesis/properties of non-linear structures (graft, miktoarm star, star and dendrimers), as well as their potential hightech applications including drug/gene delivery, electronics and energy harvesting devices. The aim of this review is to present the primary strategies for the synthesis of PVDF-based polymer materials with CMAs and critically discuss the generation of avenues that may facilitate their commercialization. We anticipate shortly that PVDF-based CMA polymers will play a progressively important role in materials science and nanotechnology, both in academia and industry.