Starch/multi-walled carbon nanotube (MWCNT) films were prepared by casting using an ionic liquid (1-ethyl-3-methylimidazolium acetate, [emim+][Ac-]) as plasticizer for the first time. The effect of the MWCNT content (0.25-5 wt.%, with respect to the sum of starch and plasticizer mass) on thermal, mechanical and electroconductive behavior of the films was studied. Films containing 0.5 wt.% MWCNT showed increases of 327 % in maximum tensile strength, 2484 % in Young's modulus and 82 % in elongation at break. The significant improvements are explained by the good MWCNT dispersion in the matrix and by the effect of [emim+][Ac-] as an efficient plasticizer, which leads to higher extensibility. The MWCNT/[emim+][Ac-] combination have a synergistic effect on film electrical conductivity, increasing a 130% (3 wt.% MWCNT). These films, easily prepared by a "green" process, have potential applications in the packaging industry but also in the field of lithium batteries, fuel cells and dye-sensitized solar cells.