Suberin is a biopolymer that acts as a barrier between plants and the environment. It is known to be a complex polyester based on glycerol and long-chain α,ω-diacids and ω-hydroxyacids. How these monomeric units are assembled at a macromolecular level remains mostly unknown. The knowledge gathered in the last 10 years has opened new insights into suberin structure. Suberin oligomeric blocks have been obtained after the partial depolymerization of the biopolymer, and in-situ studies by solid-state 13C NMR spectroscopy have shown different molecular domains and how they are spatially related. Based on these latter developments, a model is proposed for the suberin macromolecular structure. The uniqueness of the suberin polyester opens perspectives for its use as a source of bio-based materials.