A multilayer organic thin film includes a plurality of biaxially-oriented layers, where each layer is characterized by mutually orthogonal refractive indices, n1≠n2≠n3. In example structures, the corresponding in-plane refractive indices of adjacent layers may be rotated with respect to each other by a predetermined angle. Such a multilayer may be incorporated into a circular reflective polarizer, for example, which may be used in display systems to provide high broadband efficiency and high off-axis contrast. In an example process, individual organic thin films may be molded, and then oriented and stacked to form a multilayer.