Molecular solar thermal (MOST) fuels have attracted enormous research enthusiasm in solar energy conversion and storage, which can generate high-energy isomers upon harvesting photon energy and release heat on demand through reversible isomerization of molecular photo-switches such as azobenzene. However, the pristine azobenzene suffers from limitations like low energy density, short half-life and narrow absorption waveband. Recently, numerous azobenzene-based MOST fuels have been developed by various strategies including molecular engineering and template self-assembly to enhance the storage capacities, among which azobenzene-containing polymers (i.e., ‘azopolymers’) are the most promising materials for the development of MOST fuels. In this review, the state-of-the-art advances in azopolymer MOST fuels are systematically summarized. The critical parameters of azobenzene-based MOST fuels are highlighted. Various kinds of azopolymers for solar thermal energy storage and release such as azobenzene compound/polymer composites, linear azopolymers, dendrimer azopolymers, and other types of azopolymers are addressed. The most promising advantages and challenges of azopolymers for MOST fuels are analyzed, and emerging strategies as well as opportunities for future development are discussed with the goal to promote future development of MOST fuels towards innovative applications.

分子太阳能热（MOST）燃料在太阳能转换和存储方面吸引了巨大的研究热情，它可以在收集光子能量时产生高能异构体，并通过偶氮苯等分子光开关的可逆异构化按需释放热量。然而，原始偶氮苯存在能量密度低、半衰期短、吸收波段窄等局限性。近年来，通过分子工程和模板自组装等多种策略开发了许多基于偶氮苯的MOST燃料，以提高存储容量，其中含偶氮苯的聚合物（即“偶氮聚合物”）是最有前途的开发材料大多数燃料。在这篇综述中，系统地总结了偶氮聚合物 MOST 燃料的最新进展。重点介绍了偶氮苯基 MOST 燃料的关键参数。涉及用于太阳能热能储存和释放的各种偶氮聚合物，例如偶氮苯化合物/聚合物复合材料、线性偶氮聚合物、树枝状偶氮聚合物和其他类型的偶氮聚合物。分析了偶氮聚合物在 MOST 燃料中最有前景的优势和挑战，讨论了新兴策略以及未来发展机遇，旨在促进 MOST 燃料未来向创新应用的发展。