The supramolecular assemblies of sandwich-type complex Eu(TPyP)Pc (TPyP: tetrapyridylporphyrin; Pc: phthalocyanine) were fabricated at the air/water and air/Cd 2+ aqueous solution interfaces. One-dimensional columns and two-dimensional coordinate framework were formed, respectively, and characterized by surface pressure–area (π–A) isotherms, UV–vis spectra and polarized UV–vis spectra. The orientation angle of macrocycles with respect to the substrate surface is about 38° and 32° for the Langmuir–Blodgett films from pure water and Cd 2+ subphase surfaces, respectively.