Considering the hazardous use of synthetic pesticides in vegetable production in urban West Africa, this research investigated the marketing potential of organic vegetables in the food vending sector of Cotonou (Benin), Accra (Ghana) and Ouagadougou (Burkina Faso). Certified organic production and marketing was examined as a potential strategy to improve chemical food safety. A stratified random sampling strategy was applied to study the preferences of food vendors (n = 180) and consumers (n = 360); vegetable use, risk perception, choice preferences and willingness-to-pay (WTP) for organic certification were specifically analyzed. The results showed that awareness of chemical contamination risks was generally low. Appearance of a product was central to vendor choice; consumers attributed similar utility to taste and organic certification. Consumer WTP was calculated to be a premium of 1.04 USD (per plate) if the food served contained only certified organic vegetables. In restaurants, this would mean an average premium of 19% for a meal. If certified organic vegetable production is to make a positive impact on food safety in urban West Africa, we suggest concentrating marketing efforts on the educated “elite” who frequent restaurants. However, considering that restaurant owners exhibited a lower preference for organic certification than lower class food vendors, the marketing situation is difficult. We therefore conclude that demand from the food vending sector alone will not institutionalize domestic certification mechanisms; this underlines the need for public commitment to facilitating such change.