Various land-use transitions in the tropics contribute to atmospheric carbon emissions, including forest conversion for small-scale farming, cattle ranching, and production of commodities such as soya and palm oil. These transitions involve fire as an effective and inexpensive means for clearing. We applied the DECAF (DEforestation CArbon Fluxes) model to Mato Grosso, Brazil to estimate fire emissions from various land-use transitions during 2001–2005. Fires associated with deforestation contributed 67 Tg C/yr (17 and 50 Tg C/yr from conversion to cropland and pasture, respectively), while conversion of savannas and existing cattle pasture to cropland contributed 17 Tg C/yr and pasture maintenance fires 6 Tg C/yr. Large clearings (>100 ha/yr) contributed 67% of emissions but comprised only 10% of deforestation events. From a policy perspective, results imply that intensification of agricultural production on already-cleared land and policies to discourage large clearings would reduce the major sources of emissions from fires in this region.