This review explains how scientists use a special type of microscopy called solid-state NMR to study the protective outer layers of fungi and plants. The research shows that fungal pathogens can cleverly rearrange their cell walls to resist antifungal medicines, and that plants carefully organize their cell walls during growth by forming specific connections between different molecules. Understanding these structures at the molecular level could help develop better antifungal treatments and improve how we use plant biomass for biofuels and materials.