Polymers containing arabinoglucuronoxylan, fucogalactoxyglucan, pectin and arabinogalactan proteins were obtained from PAK isolated from Norway spruce with 7 % KOH. The pectin core of PAK-I2-F-1 and PAK-I2-F-2 was dominated by RG-I, as treatment with 1,4-α-D-polygalacturonase resulted in almost complete removal of homogalacturonan. Interestingly, the above has not affected the co-fractionation of arabinoglucuronoxylan (AGX), arabinogalactan proteins and rhamnogalacturonan I (RG-I). Since pectin was mainly represented by RG-I, we concluded that xylan is specifically associated with RG-I. Correlations in the HMBC spectrum demonstrate intermolecular interactions between the α-L-Rhap (RG-I) and the Xyl (xylan), indicating a covalently bound AGX:RG-I complex via the Xyl-(1→4)-Rha bond: …→2)-[(2,4-β-D-Xylp)-(1→4)]-[(α-D-GalpA-(1→2)]-α-L-Rhap-(1→4)-α-D-GalpA-(1→…. In PAK-H1-1-F-1 and PAK-H1-1-F-2, parts of RG-I and xylan were removed by enzymolysis. Part of the xylan was probably attached to the above-mentioned RG-I blocks. The removal of part of RG-I, xylan and the disappearance of the signal in the HMBC spectrum indicating the bond between RG-I and xylan confirms that part of the arabinoglucuronoxylan is covalently bound to RG-I. The observed glycosidic linkage contradicts the dominant PCW model in which pectin and hemicellulose polysaccharide networks are considered as independent components. It can be concluded that alkali-soluble xylan from Norway spruce was detected both in the free state and covalently bound to pectin.