To address the low success rate of droplet separation and the inaccurate daughter droplet volume on the square electrode, a digital microfluidic chip with fan-shaped electrode was proposed and its separation effect was studied. After analyzing the factors affecting droplet separation on the square electrode, the fan-shaped electrode was designed in combination with the advantages of crescent electrodes, dumbbell electrode, and bow electrodes. Compared with traditional separation, the novel chip can adjust the initial position of the droplets before separation to ensure the smooth shrinkage of the droplet during the separation process and improve the success rate and precision of the droplet volume. Deionized water was used as the experimental object to verify the separation effect of the novel chip. The results show that the success rates of droplet separation at different channel heights on novel electrodes are higher than that on conventional electrodes. The average error of daughter droplets is controlled at ±2%, and the coefficient of variation is as low as 1.83%. The separation accuracy can be further improved by reducing the size of the separation electrodes. The experimental results indicate that the separation success rate and splitting precision on digital microfluidic chip with fan-shaped electrode was significantly improved.