<p>Pool boiling is a fundamental heat transfer process with wide-ranging applications in electronics cooling, energy conversion, and power systems. However, its performance is often constrained by the inherent limitations of the heat transfer coefficient (HTC) and critical heat flux (CHF). To address these challenges, extensive research has focused on tailoring surface characteristics through advanced microstructural modifications. This review consolidates and critically evaluates recent progress in chemical treatments, mechanical patterning, nanostructuring, and laser-based fabrication methods designed to improve pool boiling efficiency. The discussion encompasses surface modifications across macro-, micro-, and nanoscales, highlighting structural configurations such as cavities, grooves, channels, fins, and hybrid architectures that integrate multiple geometries. By comparing modified surfaces with conventional smooth counterparts, the review identifies key mechanisms responsible for performance enhancement, including increased density of nucleation sites, capillary-assisted liquid replenishment, vapor bubble departure control, and improved wettability. Notably, laser surface texturing and hybrid micro/nanostructured surfaces consistently demonstrate superior outcomes, with reported HTC enhancements of up to threefold and CHF improvements exceeding 100% under optimized conditions. Beyond summarizing experimental findings, the review emphasizes critical considerations for practical deployment. Scalability of fabrication methods, compatibility with diverse materials such as metals and ceramics, and long-term durability under repeated thermal cycling are assessed as essential factors for industrial integration. Furthermore, attention is given to the potential trade-offs between fabrication complexity, cost, and achievable thermal gains. Overall, this review highlights the transformative potential of microstructural surface engineering in advancing pool boiling performance. Bridging fundamental mechanisms with technological applications provides a comprehensive framework to guide future research and innovation. The findings suggest that next-generation boiling heat exchangers, enabled by tailored surface designs, could deliver compact, energy-efficient, and high-reliability thermal management solutions for emerging fields ranging from microelectronics to renewable energy systems.</p>