In virtue of the rising demand for metal-free polymeric materials, organocatalytic polymerization has emerged and blossomed unprecedentedly in the past 15 years into an appealing research area and a powerful arsenal for polymer synthesis. In addition to the inherent merits as being metal-free, small-molecule organocatalysts have also provided opportunities to develop alternative and, in many cases, more expedient synthetic approaches toward macromolecular architectures, that play a crucial role in shaping the properties of the obtained polymers. A majority of preliminary studies exploring for new catalysts, catalytic mechanisms and optimized polymerization conditions are extended to application of the catalytic systems on rational design and controlled synthesis of various macromolecular architectures. Such endeavors are described in this review, categorized by the architectural elements including chain structure (types, sequence and composition of monomeric units constituting the polymer chains), topological structure (the fashion different polymer chains are covalently attached to each other within the macromolecule) and functionality (position and amount of functional groups that endow the entire macromolecule with specific chemical, physico-chemical or biological properties).

由于对无金属聚合材料的需求不断增长，有机催化聚合在过去15年中出现并空前发展，成为一个有吸引力的研究领域和强大的聚合物合成武器库。除了无金属的固有优点外，小分子有机催化剂还提供了开发替代方法的机会，并且在许多情况下，更有利于合成大分子结构的合成方法，这些方法在塑造所得聚合物的性能方面起着至关重要的作用。 。探索新催化剂，催化机理和优化聚合条件的大多数初步研究已扩展到催化体系在各种高分子结构的合理设计和受控合成上的应用。在这篇评论中描述了这些努力，