Various optically active polymers are known to afford sophisticated chirality-related functionalities, i.e. asymmetric catalysis, chiroptical switching and memory in UV-vis-NIR region, chromatographic separation of enantiomers, and sensors for molecular chirality. Recently, material researchers are received much attention to design chiral supramolecular architectures from achiral polymers upon intermolecular interactions with help of greener biosources. The present article reports an instantaneous generation of ambidextrous supramolecules revealing light-driven chiroptical switching/memory in UV-vis region when achiral azobenzene-containing vinylpolymers are non-covalently interacted with alkyl ester derivatives of natural cellulose and D-/L-glucose. It was recognized that the semi-synthetic biomaterials efficiently work as chirality-inducing scaffoldings to several achiral and optically inactive molecules, oligomers, and polymers. Our successful results shed light on a new approach of how inexpensive poly-/mono-saccharide derivatives can afford supramolecular chiroptical systems with the azobenzene pendant polymer as aggregates in suspension and liquid-crystalline films with minimal energy, time, and cost.