Sub-Saharan Africa is seeing rapid urbanization, with the population of cities such as Lagos and Nairobi growing at a rate of 3–4% a year. The region is extremely under-sampled for all air pollutants, particularly VOCs, which are useful markers for source apportionment as well as toxic in their own right. There are many contributors to air pollution in the region, and studies examining fine particulate pollution implicate traffic as the primary source in urban areas. In this pilot study, VOCs were analysed at a selection of roadside and urban background locations in Nairobi and Lagos, and 74 VOCs were quantified. GC×GC–MS/FID analysis revealed all locations were dominated by hydrocarbons typical of vehicle emissions, with the aromatic hydrocarbons benzene and toluene among the most abundant VOCs. Typical personal exposure scenarios for citizens of the cities were calculated to far exceed those of a resident in a city in Europe/US. Finally, the calculated ozone forming potential of the VOCs measured was found to be similarly high to other large cities studied with similar air pollution problems. Further study is therefore essential to determine the full extent of VOC pollution in the region and its impact on tropospheric chemistry.