Epoxides are a major family of building materials for a variety of heterochain polymers that are of wide interests and great utilities in both academia and industry. Evolving the chemical tools for ring-opening (co)polymerization (ROP or ROCP) of epoxides and synthesis of epoxide-derived macromolecular structures have thus constituted a crucial part of synthetic polymer chemistry. Limitations can be broken and vigor be infused into this long-established field when it meets with the recently revived organocatalytic methods. In this feature article, the main organocatalytic systems applied to the ROP of epoxides are briefly described in terms of catalysts, mechanisms, and control over macromolecular characteristics. Then efforts made on diverse macromolecular architectures through epoxide-based organocatalytic (co)polymerization are specially summarized and discussed. Apart from synthesis of (co)polyether structures from ROP of epoxides, emphasis is also put on copolymer structures derived from epoxides and other types of compounds including vinyl monomers, cyclic esters, cyclic anhydrides, etc., through organocatalytic ROCP. (C) 2018 Elsevier Ltd. All rights reserved.