The influence of ionic complexes on phase behavior of PS-b-PMMA copolymers over a wide range of molecular weights and PS volume fractions was investigated by small-angle X-ray scattering (SAXS), grazing incidence small-angle X-ray scattering (GISAXS), transmission electron microscopy (TEM), and neutron reflectivity (NR). The disorder-to-order transition (DOT) in both symmetric and asymmetric copolymers indicates that the overall Flory-Huggins segmental interaction parameter, chi(eff) between polystyrene (PS) and poly(methyl methacrylate) (PMMA) blocks with lithium-PMMA complexes is increased compared to that of the neat copolymers. This enhanced chi(eff) further results in an order-to-order transition (OOT), from spheres to cylinders, and an increase in the ordering and spacing of microdomains. Moreover, transitional metal ionic complexes, such as copper-PMMA complexes, are found to have the similar influence on phase behavior of PS-b-PMMA copolymers. The formation of ionic complexes in the copolymers not only offers a parameter to tune the degree of microphase separation of PS-b-PMMA copolymers but also provides a way to fabricate multifunctional materials.