The structures of alpha, beta and gamma per-azido cyclodextrin Langmuir-Blodgett films were compared using scanning force microscopy. At the micrometre scale, the crystalline nature of the beta derivative films is clearly observed, whereas alpha and gamma derivative films are more continuous. At the molecular scale, the hexagonal arrangement of the beta derivative films is easily imaged, whereas alpha derivative films are imaged with difficulty, and the images obtained with gamma derivative films have poor quality. At an intermediate scale, hexagonal superstructures can be observed with the beta derivative.