A two-component film technique at the air-water interface has been used for fabricating matrix stabilized azobenzene J-aggregates. Langmuir monolayers of (E)-1-(3-chloro-4-(alkyloxy)phenyl)-2-phenyldiazene (CnCD, n = 8, 10, 12) have been prepared with stearic acid (STA) as the two-dimensional matrix. Miscibility studies at a molecular level, explored from the monolayer pressure-area isotherms revealed a phase separation of the CnCD from the stearic acid matrix at a compression pressure of 10 mN/m. A 43-nm strong red shift in the 350 nm pi-pi* absorption feature implied formation of highly ordered J-aggregates of C(n)CDs in conformity with atomic force microscopy and micro-Raman spectral characteristics. While a one-component CnCD failed to form a 2D monolayer, the STA supported CnCD binary system crossed a mixed monolayer phase followed by compression, leading to the formation of matrix stabilized CnCD J-aggregates. (c) 2006 Elsevier Inc. All rights reserved.