Molecular self-assembly offers an effective method to modify the surface properties of common biomaterials by presenting biologically relevant chemistry in a controlled, ordered fashion. This work reports on self-assembling triblock molecules containing rigid cholesteryl segments followed by flexible oligomers of L-(lactic acid) and second generation L-lysine dendrons. Second harmonic generation and small angle X-ray scattering indicate these molecules self-assemble into multilayer polar structures when cast from ethyl acetate solutions and segregate into polar polydomains when annealed. These self-assembled layers significantly improve water wettability when coated onto poly(L-lactic acid) fibers. Scaffolds formed from fibers modified by self-assembly enhance adhesion of 3T3 mouse calvaria cells and produce greater population growth rates. These results demonstrate the use of self-assembly to present biologically relevant chemistry on surfaces of biomaterials. Applications of this technology include the modification of substrates for cell culture, tissue engineering, and cell transplantation.