External field driven fluid manipulation, in particular electric field, offers the advantages of real-time control and exceptional flexibility, rendering it highly promising for applications in microfluidic devices, liquid separation and energy catalysis. However, it is still challenging for controlled liquid transport and fine control of droplet splitting. Herein, we demonstrate a strategy to achieve direction-controlled liquid transport and fine droplet splitting on an anisotropic groove-microstructured electrode surface via an electrically switched asymmetric interface. The balance of asymmetric capillary force generated by microstructures and electro-capillary force is critical in determining directional liquid transport and fine droplet splitting. Asymmetric bubbles generated by liquid electrolysis form an asymmetric liquid-gas-solid interface and result in gradient liquid wetting behavior on the two neighboring electrode surfaces. The electric field further enhances the asymmetric wetting of a liquid droplet on the electrode surface, exhibiting electric field direction-dependent motion. Moreover, the groove-microstructured electrode surface can strengthen the liquid droplet anisotropic wetting and correspondingly refine the volume range of the splitting sub-droplet. Even unidirectional/bidirectional liquid droplet transport can be controlled in collaboration with the asymmetric groove-microstructure and electric field. Thus, this work provides a new route for liquid transport and droplet splitting, showing great potential in controllable separation, microreaction and microfluidic devices.