Non-hydrogenated amorphous Silicon-Germanium (a-SiGe) thin films were deposited at two different base pressures by RF magnetron co-sputtering. Moreover, an ex-situ thermal annealing was carried out to investigate the material properties to be suitable as the bottom cell of multi-junction solar cells. Compositional study of the films using EDX showed Ge-rich thin films with 75 atomic% of Ge. XRD reflection study implied that all samples were entirely amorphous in nature. However, a significant improvement of morphology possibly due to low base pressure was observed while thermal annealing caused peening and reduction of surface inhomogeneity in both as-sputtered films. UV-VIS-IR analysis confirmed the FESEM results. The highest transmittance was observed in the as-deposited sample grown at 4×10−5 Torr, which however reduced after thermal annealing. Tauc’s model was implied for band gap determination and band gap energy as low as 1.07 eV was found in the annealed sample grown at lower base pressure (4×10−6 Torr). Electrical properties of films were investigated by Hall effect measurement system and results found the reduction of resistivity with the same trend of optical band gap energy.