An optical stack (400) having a plurality of alternating polymeric layers (401, 402) is described. The alternating layers may be alternating birefringent (syndiotactic polystyrene, sPS) and isotropic (CoPENa) layers, or alternating positively and negatively birefringent layers. Birefringent layers are made using polymers which form optically symmetrical crystallites upon stretching of the polymer. The optical stack has a large refractive index difference in the x-direction (the stretching direction) and small refractive index differences in the y- and z-directions (the non-stretching directions). The optical stack can be made using standard film tentering methods and may be a multilayer reflective polarizer.