Nucleobase-grafted polycaprolactone has been prepared which exhibits amorphous nature, rapid photoresponse and controlled surface properties in the solid state owing to the formation of uracil-diamidopyridine (U-DAP) pairs by induced physical cross-linking. In addition, they can self-organize to alter material behavior with light, switching both optical and thermal properties. Remarkable changes in the surface morphology and the contact angle with water were also observed.