The surface modification of Li powder was attempted in order to enhance the electrochemical properties of the electrodes used in rechargeable batteries. To create a “native” LiF film on Li powder, Li powder was manufactured using a droplet emulsion technique (DET) process by introducing fluoride as a surfactant. The surface modification of the Li powder was confirmed by means of X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray analysis (EDX). Two-electrode cells (Li symmetric cells) were prepared for the purpose of impedance analysis and scanning electron microscope (SEM) observation. From the impedance analysis, the modified surface film was found to have a smaller resistance than the bare Li powder surface. SEM images showed that dendritic formations were more highly suppressed when the compacted Li powder and surface-modified Li powder electrodes were used than when the Li foil electrode was used. Moreover, the surface-modified Li powder electrodes suppressed dendritic formations more effectively than regular Li powder electrodes.