Sustainable industry practices and circular economy concepts encourage the transformation of production waste into by-products. Saccharomyces cerevisiae is widely used in fermentation industry worldwide, generating large amounts of spent yeast which is mainly directed to animal feed or discarded as waste. Instead of becoming and environmental problem, spent yeast can be directed to the extraction of valuable compounds such as mannans and mannan oligosaccharides (MOS). This review presents a compilation of the studies up to date regarding the different chemical, enzymatic, mechanical or physical processes addressed for mannans extraction and MOS production. Additionally, the existing studies on the chemical modification of mannans aimed to improve specific characteristics are also discussed. Finally, the more relevant bioactivities and potential applications of mannans, MOS and mannose are presented, together with products on the market containing these compounds.