High crystallinity GeSn substitutional alloy thin films with up to 8.7 at.% Sn are directly grown on amorphous SiO2 layers at low crystallization temperatures of 370~470 °C for potential applications in 3D electronic-photonic integration on Si as well as inexpensive virtual substrates for tandem solar cells. The optimal Ge0.913Sn0.087 thin film demonstrates a strong (111) texture and an average gain size of 10 μm, and its grain boundaries are mostly twin and low-angle boundaries with low densities of defect recombination centers. The 8.7 at.% Sn incorporated substitutionally into the Ge lattice far exceeds the ~1 at.% equilibrium solubility limit. Correspondingly, the direct band gap is significantly red-shifted from 0.8 eV for pure Ge to ~0.5 eV for crystalline Ge0.913Sn0.087, right at the verge of the indirect-to-direct gap transition that occurs at 8-10 at.% Sn alloying. Optoelectronic properties are greatly enhanced due to this transition.