Maytenus ilicifolia Mart. ex Reissek (Celastraceae) is a medicinal plant locally known as "espinheira-santa". Its leaves are widely used as a tea (infusion) for effective treatment of stomach ulcers and gastritis. Many herbs used in popular medicine have been reported to contain polysaccharides possessing a great variety of suggested biological activities. Here, we report the isolation and structural characterization of two arabinogalactans from M. ilicifolia leaves: one was extracted with hot aqueous 2% KOH (KOH-AG) and the other by infusion (Infusion-AG). The KOH-AG had Mw = 87 Kg/mol, and showed Ara, Gal, GalA, and Rha in a 69:20:6:5 molar ratio. Methylation analysis, partial acid hydrolysis, and ¹³C NMR spectroscopy indicated that it was an arabinogalactan containing a (1®4)-linked b-Galp main chain, substituted at O-6 with Araf units, which were in turn substituted at O-5, O-3, O-3,5, and O-2,5. The Infusion-AG presented Mw = 11 Kg/mol, and showed Ara, Gal, GalA, 4-O-Me-GlcA, Rha, and Glc in a 42:41:6:5:4:2 molar ratio. Methylation analysis, controlled Smith degradation, and ¹³C NMR spectroscopy showed that it was an arabinogalactan containing a (1®3)-linked b-Galp main chain, substituted at O-6 by (1®6)-linked b-Galp chains, which were mainly substituted in turn at O-3 by (1®5) and (1®3)-linked Araf chains, and non-reducing end-units of a-Araf and 4-O-Me-GlcpA. The (1®4)-linked GalA, plus 2-O- and 2-4-di-O-substituted Rhap residues were present in both arabinogalactans, strongly suggesting that they are probably linked to O-4 of some Rhap units of a type I rhamnogalacturonan, formed by repeating (1®4)-a-D-GalpA-(1®2)-a-L-Rhap groups. Arabinogalactans are classified according to their main chains, one can infer from our results that KOH-AG and Infusion-AG are type I and type II arabinogalactans, respectively.  The arabinogalactans are polysaccharides known for their biological activities, including anti-ulcer activity. It is interesting that a popular hot aqueous extraction procedure (infusion) is able to liberate them from M. ilicifoia leaves.