Climate change mitigation is a top priority for the global community. Efforts to decarbonize the world’s energy economy constitute an essential component of the mitigation process. However, transforming the energy economy primarily into renewable sources and phasing out fossil fuels completely in the next several decades may not be realistic. In fact, projections suggest that fossil fuel usage is expected to grow into the mid-century, and possibly beyond. At the same time, rapid deployment and integration of intermittent renewable sources into the electric grid depends, among other factors, on availability and access to adequate capacities for energy and electricity storage, and this aspect is lacking globally. Transitioning into a sustainable energy future will require time, scale, and speed in advancing clean technologies to achieve significant reductions in CO2 emissions. In the meantime, we rapidly need to deploy carbon capture technologies at the giga-ton scale, implement large-scale negative emission measures, and develop advanced power generation with total carbon capture. This chapter is devoted to address the latter topic and provides an overview of high-temperature fuel cells for efficient and environmentally “clean” power generation from fossil fuels with capture-ready production of CO2 without the need for post-separation from flue streams.