The mixing ratio dependence of the morphology of a polyion complex micelle formed of an anionic neutral double-hydrophilic block copolymer (AP) and a cationic-neutral double-hydrophilic block copolymer (MP) in 0.1 M aqueous NaCl solution was investigated by using small-angle X-ray scattering (SAXS), electrophoretic light scattering (ELS), and isothermal titration calorimetry (ITC), under the condition that the anionic and cationic block chains are much longer than the neutral block chains. When the anionic and cationic monomer units in the solution are nearly equimolar, the net charge of the polyion complex micelle is close to zero, and the bilayer vesicle is formed. However, when the anionic or cationic monomer units in the solution are richer than the other, the polyion complex micelle is charged by including the excess block copolymer component to form the smaller spherical micelle. The morphology transition between the vesicle and spherical micelle can take place reversibly by simply adding AP or MP into the micellar solutions. The electrostatic energy of the micelle may induce the morphology transition.