A series of Si1−xGex (x = 1, 0.848, 0.591, 0.382, 0.209, 0.064, 0) thin films prepared by ion beam sputtering were implanted with Fe ions to different doses using the metal vapor vacuum arc technique. X-ray absorption fine structure (XAFS) was used to characterize the local microstructure around the Fe atoms in Fe-doped Si1−xGex samples. Structural analysis showed that for annealed samples of Ge-rich thin films (including pure Ge) implanted with low doses of Fe ions, almost all the Fe ions substituted at Ge sites. However, an anti-ferromagnetic Fe6Ge5 impurity phase existed in the annealed samples implanted with high doses of Fe. It was also found that the solubility of Fe ions was highest in pure Ge films and that with increasing Si concentration, the solubility decreased. Magnetic analysis showed that for the as-implanted and annealed samples of Ge-rich thin films implanted with Fe ions, room-temperature ferromagnetism was strongest in the pure Ge series of samples and that as the Ge concentration decreased, the ferromagnetism at room temperature weakened. In addition, annealing could increase the number of Fe ions at substitution sites, which resulted in the observed increase in the saturated magnetization after annealing. Experiment and theoretical analysis showed that the ferromagnetism of Fe-doped Ge-rich Si1−xGex thin films samples originated from the s, p–d exchange interactions between the Si1−xGex matrix and those Fe ions which substituted at Ge sites and that the ferromagnetism was mediated by carriers.