The competitive adsorption of phenolic acids, secoiridoids, and flavonoids in a molecularly imprinted polymer (MIP) functionalized with 4vinylpiridine (4VP) moieties is analyzed here considering vanillic acid, oleuropein, and quercetin as reference molecules. Measured adsorption isotherms highlight a much stronger binding capacity of the quercetin-MIP particles toward quercetin as compared with vanillic acid and oleuropein. The acquired data were used to design and scale-up sorption/desorption processes aiming at the fractionation of olive leaf extracts. We show that a simple adsorption process, avoiding many pre-preparation steps, is possible when working at a high extract concentration due to the strong binding capacity of the MIP for flavonoids, even when using aqueous mixtures with a large alcoholic content. Solvent-gradient/temperature-swing desorption led to a sequence of fractions with enrichment of non-flavonoids at low alcoholic content while glycosylated flavonoids were enriched in fractions with 40% < alcohol content < 80%. Enrichment factors of 13 and 12 were measured for luteolin-7-O-glucoside and apigenin-7-O-glucoside, respectively. Flavonoid aglycones were enriched in fractions with alcohol content >80% (enrichment factors >20 for luteolin and quercetin). The findings reported here demonstrate the usefulness of the developed materials and sorption/desorption conditions for agricultural residue valorization and circular bioeconomy.