The combination of solubility, coded pairing and adjustable flexibility make DNA a unique polymer for designing highly-controlled self-assembled complex nanostructures and novel materials. The same tools can be exploited to produce DNA-based systems enabling the exploration of challenging topics in soft matter physics. In the talk I will exemplify this approach by describing experiments and results in which DNA assembly was used to study living polymerization, liquid crystal ordering, the templating of chemical reactions, and phase behavior and gelation transition of low-valence colloidal particles.