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A new fractionation process was developed to achieve valorization of fruit and vegetable pomaces. The importance of the residues from fruits and vegetables is still growing; therefore; the study presents the novel route of a fractioning process for the conversion of agro-industrial biomasses, such as pomaces, into useful feedstocks with potential application in the fields of fuels, chemicals, and polymers. Hence, the biorefinery process is expected to convert them into various by-products offering a great diversity of low-cost materials. The final product of the process is the cellulose of the biofuel importance. The study presents the novel route of the fractioning process for the conversion of agro-industrial biomasses, such as pomaces, into useful feedstocks with a potential application in the fields of fuels, chemicals, and polymers. Therefore the aim of this paper was to present the novel route of the pomaces fraction and the characterization of residuals. Pomaces from apple, cucumber, carrot, and tomato were treated sequentially with water, acidic solution, alkali solution, and oxidative reagent in order to obtain fractions reach in sugars, pectic polysaccharides, hemicellulose, cellulose, and lignin. Pomaces were characterized by dry matter content, neutral detergent solubles, hemicellulose, cellulose, and lignin. Obtained fractions were characterized by the content of pectins expressed as galacturonic acid equivalent and hemicelluloses expressed as a xyloglucan equivalent. The last fraction and residue was cellulose characterized by crystallinity degree by X-ray diffractometer (XRD), microfibril diameter by atomic force microscope (AFM), and overall morphology by scanning electron microscope (SEM). The hemicelluloses content was similar in all pomaces. Moreover, all the materials were characterized by the high pectins level in extracts evaluated as galacturonic acid content. The lignins content compared with other plant biomasses was on a very low level. The cellulose fraction was the highest in cucumber pomace. The cellulose fraction was characterized by crystallinity degree, microfibril diameter, and overall morphology. Isolated cellulose had a very fine structure with relatively high crystalline index but small crystallites.