Cellulose esters with varying ester and residual hydroxyl group contents represent a cheap and pliable bio-based polysaccharide to examine. In this work, the molecular organization of cellulose triacetate, cellulose acetate propionate and cellulose acetate butyrate as a response to a variety of external parameters are investigated. The morphology of ultrathin films of the cellulose esters, transferred by means of Langmuir-Schaefer (LS) deposition from the air/water interface to the surface of solid substrates, are shown to be induced by the total surface free energy of each substrate. Additionally, the spreading capability of the esters is investigated the spread of each polymer is directly linked to its chemical composition, namely the proportion of unsubstituted hydroxyl groups remaining on the glucose backbone. Monomer arrangement at the air/water interface has a distinct dependency on the rate at which their monolayers are compressed. The study provides a systematic approach to the investigations of LS deposition of cellulose esters. (C) 2015 Elsevier B.V. All rights reserved.