Energy-efficient and sustainable technologies are necessary to lower energy and carbon footprints. Many technologies are being pursued to meet the increasing energy demand in buildings. An attractive option is efficient utilization of available energy resources, including renewables, to support current and future building energy needs while targeting grid resiliency, energy, and environmental security at an affordable cost via on-site cogeneration-based approaches. This must include energy-efficient technologies with lower greenhouse gas emissions and optimized cost, performance, and reliability. This paper presents the economic and environmental benefits associated with power technologies such as thermionics and solid oxide fuel cells. Hybrid configurations consisting of heat pumps, power systems, and renewable photovoltaics in cogeneration and trigeneration modes of operation are presented. The role of such technologies in lowering CO2 emissions while improving energy resiliency and serving the needs of underprivileged communities is discussed. The key barriers of affordability and potential solutions for large-scale implementation of these promising technologies are reviewed. Case studies demonstrating the influence of power rating, electrical efficiency, design configuration, carbon dioxide intensity of the grid, and fuel on annual greenhouse gas emissions are presented for residential and commercial buildings.