Amylose triacetate was synthesized and gel permeation chromatography used to produce three fractions having different mean molecular weights. The fraction having the largest molecular weight was used to form Langmuir-Blodgett multilayers on its own and also when alternated with two different synthetic polymers. The films were characterized using X-ray diffraction, scanning electron microscopy and, in one case, second harmonic generation. Films formed from amylose triacetate alone gave no Bragg peaks. Study of alternating layers showed that amylose triacetate monolayers were about 1 nm thick as would be expected if this material takes on a helical structure.