Hybrid Langmuir and Langmuir-Blodgett (LB) films consisting of amphiphilic cyclodextrins (CDs) and hydrophobic azobenzene were fabricated. Due to the larger cross-sectional area of the CD core compared with the sum of the cross-sectional areas of the attached alkyl chains, the films had free space in the hydrophobic regions. Azo(p-Hexyl) having hydrophobic terminal chains was accommodated in the free space, whereas the usage of an azobenzene derivative bearing hydrophilic groups led to the phase separation. The average tilt angle of Azo(p-Hexyl) gave minima when the free space was just filled with Azo(p-Hexyl). Photoisomerization of azobenzenes in the hybrid LB films was studied. (c) 2005 Elsevier B.V. All rights reserved.