This work reports a simple microfluidic method for splitting a mother droplet into two daughter droplets with high and precise volume ratios. To achieve this, a droplet-splitting microfluidic device embedded with a three-dimensional (3D) conical microstructure is fabricated, in which the high splitting ratios of monodisperse mother droplets are achieved. The volume ratio of the split daughter droplets can reach up to 265. In addition, we examined factors that affect the splitting ratio of the daughter droplets and found that the ratio is affected by the flow rates of the two individual outlet channels, the injection length of the conical microstructure, and the diameter of the original mother droplets. Numerical simulations of these parameters were conducted to gain a clearer understanding of the splitting behavior. The proposed droplet splitting device with a conical microstructure enables on-chip sample extraction and droplet volume control, which can be a powerful tool for various droplet-based applications in microfluidic devices such as viral infectivity assays and sequencing heterogeneous populations.