An efficient process for saccharifying lignocellulosic biomass in concentrated aqueous solutions of certain bromine salts, particularly LiBr and CaBr2. Real lignocellulose biomass, such as corn stover, switchgrass, waste paper, hardwood, and softwood, can be hydrolyzed without the need for any prior pretreatment. Complete saccharification of both cellulose and hemicellulose is achieved within 5-200 min at temperatures ranging from about 100 to about 160° C. Residual lignin is readily separated from product sugars by filtration or centrifugation and can be used to prepare beneficial coproducts. The bromine salt can be recovered and separated from product sugars (predominantly monosaccharides) by any art-known method and in particular solvent extraction, anti-solvent precipitation, ion-exclusion chromatography and/or ion-exchange chromatography can be employed. Hydrolysis product containing sugars can be employed for in fermentation for the production of value added products or useful fuels.