Ga₂O₃/n-type 4H-SiC heterojunction diodes were fabricated by RF magnetron sputtering. The optical properties of Ga₂O₃ and electrical properties of diodes were investigated. I-V characteristics were compared with simulation data from the Atlas software. The band gap of Ga₂O₃ was changed from 5.01 eV to 4.88 eV through oxygen annealing. The doping concentration of Ga₂O₃ was extracted from C-V characteristics. The annealed oxygen exhibited twice higher doping concentration. The annealed diodes showed improved turn-on voltage (0.99 V) and lower leakage current (3 pA). Furthermore, the oxygen-annealed diodes exhibited a temperature cross-point when temperature increased, and its ideality factor was lower than that of as-grown diodes.