Semiconducting SnxSi1−x (0≤x≤0.6) thin-film alloys have been grown by pulsed laser deposition (PLD). These new materials are amorphous to X-rays and display small positive optical band gaps, suggesting potential applications in solar cells. The tin silicide films were grown by depositing very thin (1–30 Å) alternating atomic layers from individual Sn and Si targets utilizing an automated multi-target holder coupled to a conventional PLD system. The value of x was selected by controlling the thickness of the atomic layers. The films were characterized by X-ray diffraction, optical absorption, Rutherford backscattering spectroscopy, temperature-dependent resistivity, and X-ray photoelectron spectroscopy. Tin segregation is prevented by keeping the Sn layer thickness below a critical value. Compositions beyond x > 0.6 led to semimetallic SnxSi1−x films with tin crystallites.