Electrodeposition is a fundamental technology in modern society and has been widely used in metal plating and extraction, etc. However, extreme reaction conditions, including wide operation temperature ranges and corrosive media (molten salt/oxide systems as a particular example), inhibit direct in situ observation of the electrodeposition process. To visualize the electrode kinetics in such “black box,” X‐ray tomography is employed to monitor the electrochemical processes and three‐dimensional (3D) evolution of morphology. Benefiting from the excellent penetration of X‐ray, a non‐destructive and non‐contact in situ four‐dimensional (4D) visualization of Ti deposition is realized. Real‐time 3D reconstructed images reveal that the counterintuitive nucleation and growth process of a mesoscale Ti dendrite at both solid and liquid cathodes. According to 3D morphology evolution, unusual mechanism based on synergetic effect of the diffusion of metallic Ti and local field enhancement is achieved utilizing a simulation method based on a finite element method. This approach allows for timely and accurately regulating the electrodeposition process upon in situ monitored parameters. More importantly, the 4D technique upon operando X‐ray tomography and numerical simulation can be easily applied to other electrodeposition systems, which will help deeply understand the internal kinetics and the precise optimization of the electrodeposition conditions.