Biogenic volatile organic compound (BVOC) emissions were measured in a mopane woodland near Maun, Botswana in January–February 2001 as part of SAFARI 2000. This landscape is comprised of more than 95% of one woody plant species, Colophospermum mopane (Caesalpinaceae). Mopane woodlands extend over a broad area of southern Africa. A leaf cuvette technique was used to determine the emission capacities of the major vegetation and the temperature and light dependence of the emissions. In addition, relaxed eddy accumulation (REA) measurements of BVOC fluxes were made on a flux tower, where net CO2 emissions were also measured simultaneously. Large light-dependent emissions of terpenes (mostly α-pinene and d-limonene) were observed from the mopane woodland. The diurnal BVOC emissions were integrated and compared with the CO2 flux. Monoterpene flux exceeded 3000 μg C m−2 h−1 during the daytime period, comparable to isoprene fluxes and much higher than terpene fluxes measured in most areas. The terpene flux constituted approximately 25% of the diurnal net carbon exchange (CO2) during the experimental period. Other BVOC emissions may also contribute to the carbon exchange.