The aim of this review was to collate the current knowledge regarding the capacity of legumes to (1) lower the emissions of the key greenhouse gases carbon dioxide (CO2) and nitrous oxide (N2O) compared to N-fertilized systems, (2) reduce the fossil energy used in the production of food and forage, (3) contribute to the sequestration of carbon (C) in soils, and (4) provide a viable source of biomass for the generation of biofuels and other materials in future biorefinery concepts. We estimated that globally between 350 and 500 Tg CO2 could be emitted as a result of the 33 to 46 Tg N that is biologically fixed by agricultural legumes each year. This compares to around 300 Tg CO2 released annually from the manufacture of 100 Tg fertilizer N. The main difference is that the CO2 respired from the nodulated roots of N2-fixing legumes originated from photosynthesis and will not represent a net contribution to atmospheric concentrations of CO2, whereas the CO2 generated during the synthesis of N fertilizer was derived from fossil fuels. Experimental measures of total N2O fluxes from legumes and N-fertilized systems were found to vary enormously (0.03–7.09 and 0.09–18.16 kg N2O–N ha−1 , respectively). This reflected the data being collated from a diverse range of studies using different rates of N inputs, as well as the large number of climatic, soil, and management variables known to influence denitrification and the portion of the total N lost as N2O. Averages across 71 site-years of data, soils under legumes emitted a total of 1.29 kg N2O–N ha−1 during a growing season. This compared to a mean of 3.22 kg N2O–N ha−1 from 67 site-years of N-fertilized crops and pastures, and 1.20 kg N2O–N ha−1 from 33 site-years of data collected from unplanted soils or unfertilized nonlegumes. It was concluded that there was little evidence that biological N2 fixation substantially contributed to total N2O emissions, and that losses of N2O from legume soil were generally lower than N-fertilized systems, especially when commercial rates of N fertilizer were applied. Elevated rates of N2O losses can occur following the termination of legume-based pastures, or where legumes had been green- or brown-manured and there was a rapid build-up of high concentrations of nitrate in soil. Legume crops and legume-based pastures use 35% to 60% less fossil energy than N-fertilized cereals or grasslands, and the inclusion of legumes in cropping sequences reduced the average annual energy usage over a rotation by 12% to 34%. The reduced energy use was primarily due to the removal of the need to apply N fertilizer and the subsequently lower N fertilizer requirements for crops grown following legumes. Life cycle energy balances of legume-based rotations were also assisted by a lower use of agrichemicals for crop protection as diversification of cropping sequences reduce the incidence of cereal pathogens and pests and assisted weed control, although it was noted that differences in fossil energy use between legumes and Nfertilized systems were greatly diminished if energy use was expressed per unit of biomass or grain produced. For a change in land use to result in a net increase C sequestration in soil, the inputs of C remaining in plant residues need to exceed the CO2 respired by soil microbes during the decomposition of plant residues or soil organic C, and the C lost through wind or water erosion. The net N-balance of the system was a key driver of changes in soil C stocks in many environments, and data collected from pasture, cropping, and agroforestry systems all indicated that legumes played a pivotal role in providing the additional organic N required to encourage the accumulation of soil C at rates greater than can be achieved by cereals or grasses even when they were supplied with N fertilizer. Legumes contain a range of compounds, which could be refined to produce raw industrial materials currently manufactured from petroleum-based sources, pharmaceuticals, surfactants, or food additives as valuable by-products if legume biomass was to be used to generate biodiesel, bioethanol, biojet A1 fuel, or biogas. The attraction of using leguminous material feedstock is that they do not need the inputs of N fertilizer that would otherwise be necessary to support the production of high grain yields or large amounts of plant biomass since it is the high fossil energy use in the synthesis, transport, and application of N fertilizers that often negates much of the net C benefits of many other bioenergy sources. The use of legume biomass for biorefineries needs careful thought as there will be significant trade-offs with the current role of legumes in contributing to the organic fertility of soils. Agricultural systems will require novel management and plant breeding solutions to provide the range of options that will be required to mitigate climate change. Given their array of ecosystem services and their ability to reduce greenhouse gas emissions, lower the use of fossil energy, accelerate rates of C sequestration in soil, and provide a valuable source of feedstock for biorefineries, legumes should be considered as important components in the development of future agroecosystems.