Pulsed laser ablation is used to form high-quality silicon-doped β-Ga2O3 films on sapphire by alternatively depositing Ga2O3 and Si from two separate sources. X-ray analysis reveals a single crystallinity with a full width at half maximum for the rocking curve around the (−201) reflection peak of 1.6°. Silicon doping concentration is determined by elastic recoil detection analysis (ERDA), and the best electrical performance is reached at a Si concentration of about 1 × 1020 cm−3, using optimized deposition parameters. It is found that a high crystalline quality and a mobility of about 2.9 cm2 (V s)−1 can be achieved by depositing Si and Ga2O3 from two separate sources. Two types of Schottky contacts are fabricated: one with a pure Pt and one with a PtOx composition. Electrical results from these structures are also presented.