The supramolecular assembly of bis[3, 4, 12, 13, 21, 22, 30, 31-octa(dodecylthio)-2,3-naphthalocyaninato] erbium complex (Er[Nc(SC12H25)8]2) was fabricated at the air/water interface by Langmuir monolayer technique. Surface pressure-area isotherm indicates that stable monolayer is formed. The monolayer morphology on mica was investigated by atomic force microscopy (AFM). Columnar domains of ca. 100 nm ×(20-30) nm appearing in the micrograph have ordered orientation. Polarized UV-vis spectra and small-angle X-ray diffraction pattern show that the macrocycles tilt in the monolayer. The orientation angle of the naphthalocyanine ring with respect to the substrate was found to be ca. 54°. Each monolayer is ca. 3.53 nm thick. The columnar domain comprises 4-6 rows of columnar supramolecular assemblies where the molecules stack face-to-face.