What could be the self assembly behavior in aqueous solution for an amphiphilic block copolymer with a very flexible hydrophobic backbone possessing however a liquid crystalline (LC) order? To answer this question five amphiphilic block copolymers were prepared by grafting, via a thiol-ene addition reaction, four different thiol functionalized LC mesogens or LC-like side groups on two commercially available poly(ethylene oxide) block poly(butadiene) (PEO-b PB) polymers These copolymers form mono-disperse nanospheres in dilute deionized water with the aid of 1,4 dioxane as cosolvent (dioxane-H2O system), while in the THF-H2O system some give heterogeneous polydisperse micelles and others form large hollow concentric spherical vesicles ('Russian dolls arrangement) Smectic stripes inside the vesicles and the nanospheres are clearly visualized by cryo TEM technique