Cell walls from flesh, parenchyma cells, stone cells and skin were isolated from ripe and overripe Pyrus communis L. cv “De Cloche” using the phenol-buffer method. Pear polysaccharides were solubilized from cell walls by sequential extractions with aqueous solutions of ammonium oxalate, Na2CO3, and increasing concentration of NaOH, to explore overripening impact. Cell walls were also differentiated using MIR spectral data. Stone cells contained high levels of xylose and lignin while parenchyma cells had high levels of glucose, uronic acids and arabinose. Sequential extractions revealed that pear pectins had highly branched rhamnogalacturonans and were extremely methylated. Xylans were the main hemicellulose especially for stone cells. Cellulose represented about half of all cell walls. This heterogeneous composition of pear affected differently cell wall evolutions and properties. Thus, overripening involved a decrease in arabinose and a loss of pectic side chains mostly from parenchyma cells. Changes in hemicellulose and cellulose were minor.