Fermentation remains an important food preparation technique of health, cultural and economic importance throughout the world. In Sub-Saharan Africa, traditional alcoholic fermentation of cereal and non-cereal based substrates into alcoholic beverages is deeply rooted in the society. Although a multitude of traditional alcoholic beverages from cereal substrates are well researched and documented, their non-cereal based counterparts, mostly produced from indigenous, inexpensive substrates, remain less well studied. In addition, reports of health problems associated with non-cereal based alcoholic beverages produced from spontaneous fermentation are a major cause of concern. This review aims to highlight the microbiological and chemical profiles of these non-cereal based alcoholic beverages with a focus on the Sub-Saharan region. Here, we underscore the importance of the microbial repertoire and the substrates thereof in attaining aromatic complexity and a characteristic taste in these beverages. These aspects are an important starting point towards the potential commercialization of these complex aromatic non-cereal based traditional beverages.