Bolaamphiphiles with two p-amidobenzoyl azide head groups give erected monolayers on the air/water interface which have been transferred to polyacrylonitrile (PAN) surfaces. Gas phase reaction with amines converts only the outer azide group to amides, since the monolayer is crystalline. This is demonstrated by electron diffraction patterns as well as reflection-absorption infrared (RA-IR) spectroscopy of the monolayers on PAN. Subsequent UV-irradiation decomposes the remaining inner azide group to nitrenes and fixates it to the PAN subphase. It is thus possible to coat polymer surfaces quantitatively with crystalline and functional monolayers. Possible applications are shortly discussed.