Lithium metal has attracted much attention as an anode material for high-performance batteries owing to its high specific capacity and electrode potential. However, the Li metal electrode could suffer from the dendritic growth of Li during the cell operation due to the high reactivity of Li with organic electrolytes. To address this issue, we propose the use of thiourea as an electrolyte additive for Li metal-based batteries. The thiourea additive in LiTFSI/TEGDME electrolyte allowed the formation of a stable and uniform solid electrolyte interface layer on the Li electrode, thereby aiding the suppression of dendritic growth of Li and further electrolyte decomposition. Accordingly, a Li symmetric cell containing the thiourea additive exhibited six-times longer cycle life than a cell without the additive. Further, the electrolyte additive was also successfully employed in a Li-O2 cell to improve its cyclability.