The surface segregation has been found to be an appropriate method for preparing functionalized surfaces with polypeptide-b-polystyrene diblock copolymers. The preparation of stimuli-responsive surfaces containing polypeptide poly(L-glutamic acid) (PGA) segments at the surface by using amphiphilic polystyrene-b-poly(L-glutamic acid) block copolymers as surface modification agents has been demonstrated. Poly(L-glutamic acid), revealed at the surface by annealing in humid environment, has the capability of changing back and forth between a charged and a neutralized state giving a pH-responsive character to the surface. Such surfaces are currently being evaluated for different potential applications including cellular adhesion in which both surface charge density and structure are key parameters.