We demonstrate the formation, and the electronic and optical properties of a novel type of semiconductor superlattice in spontaneously ordered GaInP alloys. The most frequently observed ordered structure in MOCVD grown GaInP has CuPt symmetry where the ordering directions occur in the two B directions, corresponding to two distinct ordered variants. A new type of superlattice, termed an orientational superlattice, emerges as the ordered domains are stacked in a sequence whereby the ordering direction switches alternatively from the  direction in one domain to the  direction in the next domain. The novelty of this type of superlattice lies in that there is neither a band-gap nor an effective mass discontinuity along the superlattice axis. When the GaInP epilayer is grown on an exact (001) or A tilt GaAs substrate, the two ordered variants are equally favorable. Thus, ordered domain twins appear in ordered GaInP epilayers. We present a comparitive study between the single-variant ordered structure and the double-variant ordered superlattice structure, using TEM and time-resolved differential absorption. We show that for a same order parameter, the band-gap of an orientational superlattice is higher than that of a single-variant ordered structure, and the in-plane optical anisotropy between the  and B directions is greatly enhanced due to the superlattice effect. The experimental results are explained in terms of the band structure of the orientational superlattice.