Despite decades of research progress, ecologists are still debating which pools and fluxes provide nitrogen (N) to plants and soil microbes across different ecosystems. Depolymerization of soil organic N is recognized as the rate-limiting step in the production of bioavailable N, and it is generally assumed that detrital N is the main source. However, in many mineral soils, detrital polymers constitute a minor fraction of total soil organic N. The majority of organic N is associated with clay-sized particles where physicochemical interactions may limit the accessibility of N-containing compounds. Although mineral-associated organic matter (MAOM) has historically been considered a critical, but relatively passive, reservoir of soil N, a growing body of research now points to the dynamic nature of mineral-organic associations and their potential for destabilization. Here we synthesize evidence from biogeoscience and soil ecology to demonstrate how MAOM is an important, yet overlooked, mediator of bioavailable N, especially in the rhizosphere. We highlight several biochemical strategies that enable plants and microbes to disrupt mineral-organic interactions and access MAOM. In particular, root-deposited low-molecular-weight exudates may enhance the mobilization and solubilization of MAOM, increasing its bioavailability. However, the competitive balance between the possible fates of N monomers—bound to mineral surfaces versus dissolved and available for assimilation—will depend on the specific interaction between mineral properties, soil solution, mineral-bound organic matter, and microbes. Building off our emerging understanding of MAOM as a source of bioavailable N, we propose a revision of the Schimel and Bennett (Ecology 85:591–602, 2004) model (which emphasizes N depolymerization), by incorporating MAOM as a potential proximal mediator of bioavailable N.