Strained Sil-xGex quantum wells and multi-quantum wells, synthesized by solid source ebeam evaporated MBE on Si(100) substrates have been studied by low temperature photoluminescence (PL) spectroscopy. Phonon resolved transitions originating from excitons bound to shallow impurities in Sil-xGex layers were observed over the temperature range 2K to 100K and used to characterize Sil-xGex/Si heterostructures. Thin Sil-xGex quantum wells exhibited phonon-resolved PL spectra, similar to bulk material, but shifted in energy due to strain, quantum well width and Ge fraction. In single quantum wells confinement shifts up to ∼200 meV were observed (1.2 nm wells with x = 0.38) and NP linewidths down to 1.37 meV were obtained. The confinement shifts were modeled by hole confinement in Sil-xGex wells. An annealing study was performed to investigate the role of Si-Ge interdiffusion on luminescence. Both the geometrical shape and optical emission of the quantum well were found to significantly change through intermixing. In addition to near edge luminescence a broad band of intense luminescence was obtained from several Sil-xGex/Si heterostructures. Some layers exhibited both types of PL spectra. However, the broad PL band (peak energy ∼120meV below the strained bandgap) was predominant when the alloy layer thickness was greater than 2 - 10nm, depending on x, growth temperature, and substrate surface preparation. The strength of the broad PL band was correlated with the areal density of strain perturbations (∼109cm−2 per quantum well corresponding to a spacing of 300nm in the plane of the well; local lattice dilation ∼ 1.5 nm in diameter) observed in plan-view TEM. The first few wells of MQW exhibited only band edge luminescence as was revealed by etching off the upper MQW periods. In addition, post growth anneals at temperatures in the range 700°C to 1100°C were found to enhance band edge luminescence, while the broad luminescence band decayed to zero intensity. Interdiffusion at these these temperatures has been shown to dramatically change the QW shape and consequently interfacial asperities would be expected to disappear, consequently only shallow phonon resolved luminescence is observed in PL after annealing. The influence of PL measurement parameters such as excitation power density and PL sample temperature on the relative strengths of band edge versus broad band luminescence were also consistent with the presence of exciton traps at sites of reduced bandgap.