This work reports the first solvent-free catalytic approach for the cleavage of the fluorenylmethoxycarbonyl (Fmoc) protecting group from amine and alcohol functionalities. Various saccharide, peptide, and glyco-amino acid substrates were efficiently deprotected by simple treatment with 20 mol % neat 4-dimethylaminopyridine (DMAP) (one of the effective base catalysts found), without any solvent or stoichiometric additives. Small model structures were finally assembled through one-pot, base-catalyzed, solvent-free multistep sequences combining the Fmoc cleavage with esterification, amidation, and/or glycosylation steps.