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Surface micro/nano processing is an important method and research hotspot for enhancing the boiling heat transfer process. However, the effects of a structural gradient on a boiling surface have not been systematically studied. In this paper, we review researches that focus on porous surfaces with a structural gradient and their effects on the enhancement of boiling heat transfer and performance of phase-change devices from two main aspects: Geometric gradient and wettability gradient. Porous surfaces with a geometric (structural) gradient were divided into four series: single-layer geometric gradient structure, multi-layer geometric gradient structure, surface covered with a micro/nanolayer, and surface with a radial gradient. In addition, the surface with a wettability gradient also has a considerable improvement in boiling heat transfer. Especially, we present some of the work related to the improvement in boiling heat transfer for porous surfaces with structural gradient, which has been carried out by our research group. Honeycomb-like and forest-like porous copper surfaces are typical single-layer geometric gradient porous surfaces with excellent boiling heat transfer performance. They have abundant microstructures and sub-microstructures/nanostructures, which are favorable for vapor escaping and liquid rewetting, respectively. For all the mentioned single-layer geometry gradient porous surfaces, the critical heat flux increases as the sample thickness increases. Furthermore, we fabricated a two-layer composite porous surface (TLCS) with a honeycomb-like porous copper surface on top of a forest-like porous copper surface. This TLCS is a multilayer geometric gradient structure porous surface that can further enhance the boiling heat transfer process. The heat transfer coefficient (HTC) of TLCS is 1.5 and 1.2 times larger than those of the biomimetic copper forest and honeycomb structures, respectively. When a small current is applied to the honeycomb-like porous copper surface, the dendrites on the pore wall transferred to micro balls and a surface with a structural gradient is obtained. The modified surface is a microstructural porous surface covered by a nanolayer that further enhances the HTC (1.7 times). The diameter of the honeycomb-like porous copper surface can be controlled with a radial diameter gradient. A sample in which the diameter around the center is much smaller than that around the edge enhances the HTC 1.4 times compared with a sample with uniform diameter. When the TLCS was modified with polytetrafluoroethylene (PTFE), it became a hybrid wetting surface. The experimental results show that the wall superheat temperature at the same heat flux during the heat flux decreasing can repeat that during the heat flux increasing well within 0.5°C, demonstrating that the boiling hysteresis was successfully eliminated. As the porous surface with a structural gradient has excellent performance in boiling heat transfer, it has been widely used in phase-change devices, such as loop and flat heat pipes, to improve their functioning. An ultra-thin flat heat pipe (UTHP), which is only 0.6 mm thick, can significantly reduce the evaporator temperature by 10°C under a 6 W heat load compared with a copper plate. This paper summarizes the most relevant features related to boiling heat transfer enhancement when using structural-gradient porous surfaces and the improvements in phase-change devices that use such surfaces. Despite the advances in this aspect, the porous surfaces can be further optimized to achieve a better heat transfer performance.