Two crowned azobenzene derivatives APCM and APCN were synthesized and incorporated into a β-cyclodextrin derivative ACD. Both APCM/ACD and APCN/ACD formed a stable Langmuir monolayer at the air-water interface. MultilayerLangmuir-Blodgett (LB) films with an ordered lamellar structure were constructed from APCM/ACD and APCN/ACD monolayers which showed a nonlinear polarisability (β) of 4 × 10−29 and