Different forms of carbon (C) cycle continuously through several pools in natural and managed ecosystems and spheres. Carbon's recent "commodification," as a negative environmental externality, has rendered it a "scarce" and "tradable" element. Although C supply in nature is not limited, energy is required to make it available as a plant nutrient, assimilate it in plant tissues, and sequester it as temporary or recalcitrant C in soils. Human demand for C-based energy and plantfixed C has accelerated, and altered its global cycle, raised its atmospheric content, contributed to climate change through global warming, and impacted several provisioning, regulating, and supporting ecosystem services. Agroecosystems are both sources and sinks of C. In a carbon dioxide-constrained world, plant-fixed and sequestered C in natural and managed ecosystems has a potential role in mitigating climate change, providing C-neutral and renewable bioenergy, and positively affecting ecosystem services. Due to the intricacies of the complex, interconnected biogeochemical cycles involving C, nitrogen, and water in which soils play an important role, bioenergy crops do not provide an easy solution to climate change mitigation, they may contribute to it. This chapter presents a critical review assessing the state of knowledge, and exploring opportunities and challenges of the role of C in bioenergy crops in mitigating global climate change, while sustainably providing other ecosystem services.