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BACKGROUND: The peel from unripe banana biomass is an agroindustrial waste. The present study aimed: (i) to extract pectin from enzymatically-treated waste peel from unripe banana biomass (WPUBB) using a Box-Behnken design to optimize the extraction conditions (temperature, pH and extraction time) and obtain a maximum yield and (ii) to fractionate the polysaccharides from WPUBB employing sequential extractions using different solvents. RESULTS:The optimized product was obtained at 86 ∘ C, pH 2.00, for 6 h and it presented a yield of 11.63%. The optimized product had low galacturonic acid content and a high amount of glucose (82.3%), suggesting the presence of starch (as confirmed by the bi-dimensional heteronuclear single quantum coherence NMR spectrum). All of the fractionated polysaccharides had a high glucose content. Low amounts of pectin were found in the water, chelating and diluted alkali-soluble fractions. The fractions extracted using NaOH indicated the presence of glucuronoarabinoxylans. CONCLUSION: Glucose was the main monosaccharide found in all the fractions extracted from the WPUBB. Although the present study suggests that WPUBB is still not suitable for pectin extraction using current technologies, other compounds, such as resistant starch and glucuronoarabinoxylans, were found, suggesting that WPUBB could be used in the development of food formulations.