The monolayer behavior of bis[2,3,9,10,16,17,24,25-octakis(octyloxy)phthalocyaninato] rare earth complexes M[Pc(OC8H17)(8)](2) (M=Eu, Dy, Er) at the air-water interface and their ordered molecular assemblies fabricated by Langmuir-Blodgett technique have been investigated by a series of techniques including surface pressure-area isotherms, electronic absorption spectra, polarized absorption spectra, low-angle X-ray diffraction patterns, and transmission electron microscope (TEM). The results indicated that bis(phthalocyaninato) rare earth molecules form well-ordered stable monolayers with a face-to-face configuration and edge-on arrangement to the water surface at the air-water interface and lamellar multilayers on solid substrates. The orientation angle of phthalocyanine rings with respect to the quartz plate surface in the Langmuir-Blodgett films has been determined to be 64.6 degrees, 63.5 degrees, and 63.3 degrees for the Eu, Dy, and Er double-decker complexes, respectively, by the polarized absorption spectroscopy. High-resolution TEM reveals that a series of well-ordered rodlike aggregates of bis(phthalocyaninato) rare earth complexes, which can be considered as molecular cable arrays, were formed by self-organization in the monolayers. (c) 2005 Elsevier B.V. All rights reserved.