The ability of phenolic compounds to bind to dietary polysaccharides such as starch and plant cell wall components impacts their nutritional value. Here, we report interactions between potato cells and three different phenolic compounds (+)-catechin, phloridzin and vanillic acid. The binding interactions of the phenolic compounds with intact potato cells, as well as disrupted cells, cooked cells, isolated cell walls and starch granules was explored varying polyphenol concentration, pH and incubation time. Results showed that binding capacity depends on the type of phenolic compound ((+)-catechin>phloridzin>vanillic acid) as well as the type of substrate, to a maximum of ∼50µmol/g (dry weight). The observed differences (p<0.05) were ascribed to the amount and accessibility of potential binding sites in both the phenolic compounds and the polysaccharides. Remarkably, polyphenols could penetrate intact cells and bind the starch within them, suggesting their potential as delivery vehicles, whose loading capacity more than doubled after cooking.