We studied the phase change and resistive switching characteristics of copper oxide (CuxO) films through post-thermal annealing. This investigation aimed to assess the material's potential for a variety of electrical devices, exploring its versatility in electronic applications. The CuxO films deposited by RF magnetron sputtering were annealed at 300, 500, and 700 °C in ambient air for 4 min by rapid thermal annealing (RTA) method, and then it was confirmed that the structural phase change from Cu2O to CuO occurred with increasing annealing temperature. Resistive random-access memory (ReRAM) devices with Au/CuxO/p+-Si structures were fabricated, and the ReRAM properties appeared in CuO-based devices, while Cu2O ReRAM devices did not exhibit resistive switching behavior. The CuO ReRAM device annealed at 500 °C showed the best properties, with a resistive window of 8 × 102, good switching endurance of ~100 cycles, data retention for 104 s, and stable uniformity in the cumulative probability distribution. This characteristic change could be explained by the difference in the grain size and density of defects between the Cu2O and CuO films. These results demonstrate that superior and stable resistive switching properties of RF-sputtered CuxO films can be obtained by low-temperature RTA.