Electrode structure is an essential factor affecting the performance of flexible humidity sensors. In this study, Cu and Cu2 + 1O electrodes were printed by the one-step method using laser direct writing technology to reduce the nano–CuO ink on flexible substrate PI and to be used for a humidity sensor. The resistance of the humidity sensors with nine various electrode structures was measured under the relative humidity (RH) of 16–78%. It was observed that all sensors showed good humidity sensing characteristics, and the sensitivity of the copper-based humidity sensor was not affected by the electrode structure under low humidity conditions but was significant under high humidity conditions. The sensor with the length of 1960 μm and the width of 120 μm shows the lowest sensitivity of 180.2 KΩ/%RH under 35% RH, and the sensor with the length of 2430 μm and the width of 180 μm shows the highest sensitivity of 1744 kΩ/%RH under 65% RH. It is expected that the results can provide an assessment of the performance improvement of the flexible humidity sensor and a reference for the research and development of intelligent wearable devices.