The unremitting pursuit of high-performance and multifunctional materials has consistently propelled modern industries forward, stimulating research and motivating progress in related fields. In such materials, polybenzoxazine (PBz) aerogel, which combines the virtues of PBz and aerogel, has attracted salient attention recently, emerging as a novel research focus in the realm of advanced materials. In this review, the preparation scheme, microscopic morphology, and fundamental characteristics of PBz aerogels are comprehensively summarized and discussed in anticipation of providing a clear understanding of the correlation between preparation process, structure, and properties. The effective strategies for enhancing the performance of PBz aerogels including composite fabrication and hybridization are highlighted. Moreover, the applications of PBz-based aerogels in various domains such as adsorption (including wastewater treatment, CO capture, and microwave adsorption), thermal insulation, energy storage as well as sensors are covered in detail. Furthermore, several obstacles and potential directions for subsequent research are delineated with a view to surmounting the prevailing constraints and achieving a realization of the shift from experimental exploration to practical applications.