Most African countries have ratified the Stockholm Convention on persistent organic pollutants (POPs) and are expected to reduce emissions of POPs such as organochlorine pesticides (OCPs) to the atmosphere. Emerging evidence, however, suggests that there are contemporary sources of OCPs in African countries despite the global ban on these products. This study investigated the atmospheric contamination from OCPs in four West African countries—Togo, Benin, Nigeria, and Cameroon—to ascertain the emission levels of OCPs and the characteristic signatures of contamination. Polyurethane foam (PUF) disk passive air samplers (PAS) were deployed in each country for ca. 55 days in 2012 and analyzed for 25 OCPs. Hexachlorocyclohexanes (HCHs) and DDTs constituted the highest burden of atmospheric OCPs in the target countries, at average concentrations of 441 pg m−3 (range 23–2718) and 403 pg m−3 (range 91–1880), respectively. Mirex had the lowest concentration, ranged between 0.1 and 3.3 pg m−3. The concentration of OCPs in rainy season was higher than in dry season in Cameroon, and presupposed inputs from agriculture during the rainy season. The concentrations of ∑25 OCPs in each country were in the following order: Cameroon &gt
Nigeria &gt
Benin &gt
Togo. There was significant evidence, based on chemical signatures of the contamination that DDT, aldrin, chlordane, and endosulfan were recently applied at certain sites in the respective countries.