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.