Biochar is the carbon-rich product of the pyrolysis of biomass under oxygen-limited conditions, and it has received increasing attention due to its multiple functions in the fields of climate change mitigation, sustainable agriculture, environmental control, and novel materials. To design a "smart" biochar for environmentally sustainable applications, one must understand recent advances in biochar molecular structures and explore potential applications to generalize upon structure-application relationships. In this review, multiple and multilevel structures of biochars are interpreted based on their elemental compositions, phase components, surface properties, and molecular structures. Applications such as carbon fixators, fertilizers, sorbents, and carbon-based materials are highlighted based on the biochar multilevel structures as well as their structure-application relationships. Further studies are suggested for more detailed biochar structural analysis and separation and for the combination of macroscopic and microscopic information to develop a higher-level biochar structural design for selective applications.