Polysaccharides are highly variable and complex biomolecules whose inventory of structures is still very incomplete, as nature still preserves unexplored biotopes. Plants, macroalgae and microalgae are an integral part of the daily life of human being regardless of culture, time, or knowledge development of a country. Natural medicine is an ancestral knowledge widely distributed throughout the world, handed down for centuries from generation to generation by those commonly referred to as “nganga” healers or shamans. It is also called alternative medicine or traditional medicine, and has been associated for millennia to legends. This review gives an emphasis regarding the ethnobotanic approach associated to the structural variability of poly- and oligosaccharides for designing the new polysaccharide-based drugs and hydrocolloids of tomorrow. The guiding thread is to survey the potential of plants (and some macroalgae) from Africa as a source of polysaccharides with original structures and, secondly, to correlate these structures with biological and/or functional properties in particular to address and advance the sustainable development and economic growth of mankind.