Poly[2-methoxy-5(2'-ethylhexoxy)-p-phenylenevinylene] (MEH-PPV) has been for the first time prepared and fully characterized in enantiopure (R) form. If the polymer molecular weight is sufficiently low, (R)-MEH-PPV assumes a helical supramolecular structure in the solution aggregates, with consequences on the tendency to aggregation and on the fluorescence quenching, both of which are reduced with respect to the racemic analogue.