Alkaline treatment is a common step largely used in the industrial extraction of agar, a phycocolloid obtained from red algae such as . The subsequent residue constitutes a poorly valorized by-product. The present study aimed to identify low-molecular-weight compounds in this alkaline waste. A fractionation process was designed in order to obtain the oligosaccharidic fraction from which several glycerol-galactosides were isolated. A combination of electrospray ion (ESI)-mass spectrometry, ¹H-NMR spectroscopy, and glycosidic linkage analyses by GC-MS allowed the identification of floridoside, corresponding to Gal-glycerol, along with oligogalactosides, i.e., (Gal) -glycerol, among which α-d-galactopyranosyl-(1→3)-β-d-galactopyranosylα1-2⁻glycerol and α-d-galactopyranosyl-(1→4)-β-d-galactopyranosylα1-2⁻glycerol were described for the first time in red algae.