This paper explores the role of decentralized renewable energy (DRE) projects play as a simultaneously mitigative and adaptive response to climate change. We develop a general conceptual framework that illustrates how introducing modern energy services through decentralized renewable energy can stabilize the ecological and social determinants of climate change vulnerability, while performing a critical climate change mitigation function. This framework is developed through a high-level overview of the key implications of rural energy deprivation: deforestation and ecosystem degradation (with significant greenhouse gas emissions implications), chronic rural poverty, and high vulnerability to the negative impacts of climate change. We then explore global sustainable development pathways and the integral role that decentralized renewable energy can play in stabilizing greenhouse gas concentrations in the atmosphere at levels that would prevent dangerous anthropogenic interference with the climate system. We then describe how mitigation and adaptation synergies provide avenues for integrating sustainable development with climate policy, contextualized with respect to key relationships between the Millennium Development Goals and access to energy. We then turn to the related issue of poverty and climate change in the context of how climate stresses exacerbate poverty by impairing the ecosystem services upon which the poor rely heavily. The conceptual framework concludes with a full description of the role DREs play in rural agroecosystems, particularly how DREs can enhance the flow of regulatory and provisioning ecosystem services, and expand livelihood opportunities—all of which builds adaptive capacity for climate change. The paper concludes with some comments and recommendations for enhancing the constructive role for DRE in overcoming the perceived divide between climate change mitigation and adaptation policy.