Abstract: Benzoxazine resins, as a novel class of thermosetting polymer materials, have garnered significant attention from both academia and industry due to their unique structural designability. With the rapid advancements in high-end technological fields and the continuous enhancement of environmental awareness among humans, the future development trend of benzoxazine resins is inevitably grounded in high performance and multifunctionality with a predominant focus on sustainability. Our research team insist on the novel synthetic approach to benzoxazine molecules, aiming to explore the relationship between the molecular structure, the curing mechanisms of thermosetting resin monomers and the resulting material properties through the design and regulation of molecular structures and hydrogen bonding. We innovate high-performance benzoxazine resin systems, develop methods for optimizing the performance of sustainable bio-based thermosetting resins, and fabricate new benzoxazine-based functional materials. This paper reviews the recent progress made by our team in the high-performance enhancement, greening, and functionalization of benzoxazine resins, while also projecting future research directions for this field.