We have investigated the structural and optical properties of metastable amorphous and crystalline GeSn layers on Si substrates. The as-deposited amorphous layers crystallize during annealing at 500°C. This transition leads to a significant change in the local environment of the Sn atoms and in the optical properties. The Ge-Sn bond length is decreased after crystallization. The as-deposited GeSn layers, with nominal 4.5% and 11.3% Sn content, do not show Sn segregation. For the crystallized GeSn with nominal 4.5%, the Sn appears to be substitutional, as no Sn clustering was observed. However, for the crystallized GeSn with nominal 11.3% Sn, Sn segration and the presence of β-Sn is observed by EXAFS. A method to suppress Sn segregation and increase the substitutional Sn concentration is discussed. Furthermore, we determined the optical properties of amorphous and crystalline GeSn with nominal 4.5% Sn. The bandgap energy decreases significantly from 0.89 eV (1392 nm) ± 0.05 eV for the amorphous layer to 0.52 eV (2383 nm) ± 0.05 eV for crystalline GeSn, leading to significant reduction in penetration depth.