Thin films of homogeneous mixture of amorphous silicon and aluminum were produced with magnetron sputtering using 2-phase Al–Si targets. The films exhibited variable compositions, with and without the presence of hydrogen, aSi1−xAlx and aSi1−xAlxHy. The structure and optical properties of the films were investigated using transmission electron microscopy, X-ray photoelectron spectroscopy, UV-VisNIR spectrometry, ellipsometry, and atomistic modeling. We studied the effect of alloying aSi with Al (within the range 0–25 at. %) on the optical band gap, refractive index, transmission, and absorption. Alloying aSi with Al resulted in a non-transparent film with a low band gap (<1 eV). Hydrogenation of the films increased the band gap to values >1 eV. Variations of the Al and hydrogen content allowed for tuning of the optoelectronic properties. The films are stable up to a temperature of 300 °C. At this temperature, we observed Al induced crystallization of the amorphous silicon and the presence of large Al particles in a crystalline Si matrix.