We report the synthesis, structural characterization, and preliminary optical studies of ultrathin Ge-Si superlattices with individual sublayers smaller than the Si unit cell, grown by MBE on (001) silicon substrates. Structures are fabricated one monolayer at a time in a configuration GeGeSiSiGeGe..., resulting in either ordered alloys or complex cell superlattices. Rutherford backscattering and channeling experiments on these highly strained heterostructures indicate excellent crystallinity with tetragonal distortion as high as 3.5%. Electron diffraction patterns exhibit characteristic superlattice reflections indicative of one-dimensional layering with periodicity of four monolayers. X-ray scans along the growth direction at the (002) position in reciprocal space reveal a strong peak not observed in random GeSi alloys. This scattering is attributed indirectly to the GeSi ordered phase. The optical transition energies measured by Schottky barrier electroreflectance correspond to those expected from homogeneous alloys of the same composition; however, the width of optical transitions is less than 30 meV at room temperature, allowing a clear resolution of the splitting of the valence band by strain. Modification of the unit cell of the diamond lattice in this way should permit the design of materials with novel opto-electronic characteristics. Preliminary Raman and photoconductivity measurements are also reported.