Self-scrolled V2O5@PANI nanoribbons are obtained in one step by oxidative copolymerization of isopolivanadates and a reduced amount of anilinium salts under ambient conditions, without a hydrothermal treatment. The material reveals a unique structure consisted of nanosized V2O5–PANI “true hybrid” areas joined with conductive polymer arms providing electric transport within this hierarchic network additionally nanostructured by self-scrolling. Microporosity of the material provides an enhanced surface area of 60m2/g while the flexible polymer links allow the stable intercalation capacity of about 200mAh/g.