Negative thermal expansion (NTE) is a counterintuitive physical phenomenon that the unit cell volume of material usually contracts instead of expands upon heating. With two decades’ development, NTE has been discovered in many kinds of compounds, in which framework structure materials account for the major part. The flexible bridging linkage units and relatively large void in the crystal structure of framework structure materials facilitate the transverse vibration of atoms, resulting the intriguing NTE. A growing number of framework structure NTE materials have been discovered from the earliest studied oxides, cyanides, metal–organic frameworks (MOFs), and then to fluorides. In this paper, framework NTE materials are reviewed thoroughly in terms of chemical formulas and crystal structures, which involve oxides, fluorides, cyanides, and MOFs. The thermal expansion property of framework structure materials is closely associated with the structure character that a larger framework with more flexible bridge groups encourages a stronger NTE. Since the metal atom size impacts the volume of framework structure, the magnitude of NTE is also sensitive to the metal atom size in a specific crystal structure classification. Accordingly, control methods of thermal expansion aiming at framework structures are summarized, including chemical substitution, local structure distortion, and guest molecular or ions intercalation. As for the control of thermal expansion, chemical substitution is the most widespread method. The recently proposed method of guest molecular or ions intercalation is most effective for the thermal expansion control in large framework structures such as cyanides and MOFs. The local structure distortion shows a significant effect in fluorides, which can be extended to other systems. At last, problems and future developments of framework structure NTE materials are discussed from the aspects of discovery and design of new NTE materials, NTE mechanism, thermal expansion control, and application of NTE materials. Some strategies and ideas are proposed for the development of framework structure NTE materials.

负热膨胀 (NTE) 是一种违反直觉的物理现象，即材料的晶胞体积通常在加热时收缩而不是膨胀。经过二十多年的发展，在多种化合物中发现了NTE，其中骨架结构材料占主要部分。骨架结构材料的晶体结构中灵活的桥联单元和相对较大的空隙促进了原子的横向振动，从而产生了有趣的NTE。从最早研究的氧化物、氰化物、金属有机骨架 (MOF) 到氟化物，已经发现了越来越多的骨架结构 NTE 材料。在本文中，框架 NTE 材料在化学式和晶体结构方面进行了彻底的审查，其中涉及氧化物、氟化物、氰化物和 MOF。骨架结构材料的热膨胀特性与具有更多柔性桥组的更大骨架促进更强的 NTE 的结构特征密切相关。由于金属原子尺寸影响骨架结构的体积，NTE 的大小也对特定晶体结构分类中的金属原子尺寸敏感。据此，总结了针对骨架结构的热膨胀控制方法，包括化学取代、局部结构畸变、客体分子或离子嵌入等。至于热膨胀的控制，化学置换是最普遍的方法。最近提出的客体分子或离子嵌入方法对于大型框架结构（如氰化物和 MOF）的热膨胀控制最有效。局部结构畸变在氟化物中显示出显着影响，可以扩展到其他系统。最后，从NTE新材料的发现与设计、NTE机理、热膨胀控制、NTE材料的应用等方面讨论了骨架结构NTE材料的问题和未来发展。针对骨架结构NTE材料的发展提出了一些策略和思路。