For the development of renewable bioproducts able to solubilize organic persistent pollutant such as benzo[a]pyrene (BaP), modified potato starch was synthesized by alkylation. The addition of alkyl chains was performed with three different alkylation agents: epoxyalkane, alkenyl succinic anhydride and 1,4-butane sultone. Twelve alkylated starches were obtained with different molar substitutions (MS) and various alkyl chain lengths (to three carbons up to sixteen). The chemical structural characteristics were investigated by methods of (1)H NMR and FTIR. In comparison with the native starch, the ether modified starches showed in general an enhancement of their aqueous solubility whereas the ester modified starches stimulated the BaP aqueous solubilization. Indeed, the compounds P6 and P12, which increased 40-fold the BaP aqueous concentration, present high surfactant properties.