This review covers the operating conditions for extracting top value-added chemicals, such as levulinic acid, lactic acid, succinic acid, vanillic acid, 3-hydroxypropionic acid, xylitol, 2,5-furandicarboxylic acid, 5-hydroxymethyl furfural, chitosan, 2,3-butanediol, and xylo-oligosaccharides, from common lignocellulosic biomass. Operating principles of novel extraction methods, beyond pretreatments, such as Soxhlet extraction, ultrasound-assisted extraction, and enzymatic extraction, are also presented and reviewed. Post extraction, high-value biochemicals need to be isolated, which is achieved through a combination of one or more isolation and purification steps. The operating principles, as well as a review of isolation methods, such as membrane filtration and liquid−liquid extraction and purification using preparative chromatography, are also discussed.