Five different compounds, included here arachidic acid (AA), tri-n-octyl phosphine oxide (TOPO), a kind of long chain Schiff base (SB), 5,10,15,20-tetra-4-oxy (2-stearic acid) phenyl porphyrin (TPP(-COOH)), and a long chain ferrocene derivative (Fc), were introduced into Langmuir-Blodgett (LB) films containing luminous rare earth complex Eu(TTA)(3)Phen or Sm(TTA)(3)Phen alternating with arachidic acid (AA). The subphase used was a composite subphase : an aqueous solution saturated with 1,10-phenanthroline, 2-thenoyltrifluoroacetone, and the complex Eu(TTA)(3)Phen or Sm(TTA)(3)Phen. Low angle X-ray diffraction results show that all the LB films have a periodic layer structure. Vertical uniformity of these LB films has been demonstrated by UV-Vis and fluorescence emission spectra. Both absorbance and relative fluorescence intensity increase linearly with the number of LB layers. The results of fluorescence spectra also indicate that, TOPO and SB have a fluorescence enhancement effect on the complexes, while TPP(-COOH) and Fc have a strong fluorescence quenching effect. AA does not influence the fluorescence of the complexes.