The monolayer behaviour of a luminescent europium complex Eu(TTA)(3)Phen on three different subphase surfaces have been investigated. Reproducible pi-A isotherms and uniformly-distributed crystalline monolayers have been obtained only on the composite subphase that, here, denotes the aqueous solution saturated with Phen (1,10-phenanthroline), TTA (alpha-thenoyltrifluoroacetone) and Eu(TTA)(3)Phen. The plateau, appearing on pi-A isotherm at pi=8 mN m(-1), corresponds to the surface crystallization of Eu(TTA)(3)Phen. The whole process of surface crystallization was videotaped in situ through the Brewster angle microscopy and proved by the images as well as by the electron diffraction hexagonal patterns on the transmission electron microscopy (TEM) images. The bright pitches of microcrystals were observed within the view field of a fluorescence microscope. Moreover, before crystallization a phase separation was observed at pi approximate to 6 mN m(-1) in monolayers of Eu(TTA)(3)Phen mixed with arachidic acid (AA) through TEM. By using the composite subphase, high-quality and intensely fluorescent multilayers of Eu(TTA)(3)Phen/AA (in molar ratio 1:1) were fabricated by the Langmuir-Blodgett technique.