The current study isolated a homogeneous polysaccharide (AP) with a molecular weight of 7.9 kDa from the pomace of Fuji apples. AP was found to consists of rhamnose, galactose, arabinose, glucose, and galacturonic acid in a ratio of 4.3:5.2:2.6:1.0:11.9. Ten sugar residues in AP, including T-Araf, 1,5-Araf, 1,2-Rhap, 1,3-Rhap, T-Galp, 1,3,5-Araf, 1,4-Galp, 1,4-GalpA, 1,6-Glcp, and 1,3,6-Glcp were identified using methylation and GC-MS. Combined with 1D and 2D NMR, it was further revealed that AP possesses a backbone of α-Galp-(1 → [3)-α-Rhap-(1 → 2)-α-Rhap-(1]