This dissertation deals with the integrated sustainability assessment of next-generation perovskite photovoltaics (PVs), emphasizing their potential to advance climate-smart, resource-efficient solutions across energy and agri-food systems. In response to global sustainability challenges, including rising global warming potential, material constraints, and food-energy-water interdependencies, this research establishes a multi-scale modeling framework that integrates prospective life cycle assessment (LCA), techno-economic analysis, and high-resolution systems simulation. A perspective study defines the overarching trajectory through three pillars: the development of perovskite tandem PVs, the application of circular economy principles, and the cross-sector integration of solar technologies into agricultural infrastructure.The first set of studies applies this framework to evaluate the sustainability performance of perovskite tandem PVs. An LCA quantifies energy payback, emissions, and environmental trade-offs across a range of device configurations and efficiencies. A second study incorporates consequential life cycle modeling and partial equilibrium analysis to assess the broader systemic impacts of transitioning from silicon to perovskite PVs, including market-mediated shifts in material demand. A third study introduces circular design strategies, integrating experimental rejuvenation and recovery data with life cycle and techno-economic modeling to evaluate long-term performance and deployment viability. Collectively, these studies establish a robust foundation for assessing emerging PV technologies across material, economic, and environmental dimensions. The second part of the dissertation focuses on perovskite agrivoltaics (AgVs) as a strategic application to support climate-smart agriculture and enhance agri-food system resilience. One study evaluates open-field, centralized AgV systems within the U.S. agricultural supply chain, using spatially resolved life cycle modeling to quantify emissions, energy, and water impacts at national scale. A complementary study examines greenhouse-based, distributed AgV systems, coupling EnergyPlus simulations with LCA across diverse U.S. climates. It highlights the role of semi-transparent perovskites in improving energy efficiency, water conservation, and seasonal adaptability within controlled environment agriculture. These applications demonstrate how perovskite AgVs can simultaneously enable decarbonization, resource stewardship, and resilience in food production. Together, this dissertation advances a comprehensive methodology for evaluating and optimizing perovskite PVs as a foundation for sustainable, cross-sector transformation in energy and agriculture.