A regular two-dimensional photoluminescent array of Anderson-type polyoxometalates (POMs) was constructed as built-up Langmuir-Blodgett (LB) films. LB films of hexatungstoantimonate (SbW6) and -manganate (MnW6) were successfully fabricated by using dimethyldioctadecylammonium (DODA) as cationic partner, while hexamolybdochromate (CrMo6) was unsuccessful. Specular X-ray reflectivity (SXR) and grazing incidence X-ray diffraction (GIXD) measurements revealed that both SbW6/DODA and MnW6/DODA LB films exhibited well-ordered layers consisting of periodic arrangement of the planar-structured Anderson-type molecules. Surprising periodicity was observed in SbW6/DODA LB film, in which the distance between SbW6 and DODA layers was 4.40 nm, and SbW6 anions would form a two-dimensional square lattice with a length of 1.4 nm. SbW6/DODA LB films exhibited photoluminescence at 77 K, while emission spectra were observed at room temperature for SbW6 solid.