The synthesis, properties, functionalization, and applications of phosphorus are reviewed to reveal the challenges and opportunities facing present and future research on phosphorus‐based functional materials. The topological constructions of various phosphorus‐based functional materials are an encouraging prospect in the rapid development of nanotechnology. Abstract Tremendous progress has been made in scientific research and application of phosphorus allotropes and their hybrid materials in recent decades. In particular, nanomaterial design has emerged as a promising solution to tackle many fundamental problems in conventional materials. This review discusses phosphorus‐based functional materials from the perspective of topological structures, which have several advantages such as good chemical stability, high surface areas, adjustable particle sizes and compositions, as well as various functionalities that enable a good performance in energy storage and conversion as well as other applications. Then, the progress on these functional materials for application in batteries, supercapacitors, catalysis, field‐effect transistors, optoelectronics, flexible electronics, sensors, biomedicine, etc., is discussed and summarized as well. Special attention is given to the research efforts to overcome the inherent shortcomings faced by red/black phosphorus. The aim is to elucidate the relationship between the phosphorus‐based topological structures and their performance. Finally, this review casts an insightful outlook on the future direction of the phosphorus‐based materials in nanotechnology.

Published in: "Advanced Functional Materials".