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Alkali metal (M = Na, K) salts of the [CB₁₁H₁₂]⁻ anion have attracted increasing attention in many fields such as catalysis and all-solid-state batteries. However, tedious and low-yielding synthetic methods have seriously limited their application in these fields. We developed a facile method for the direct synthesis of the unsolvated potassium and sodium salts of the [CB₁₁H₁₂]⁻ anion in 66% and 68% yields, respectively, by reactions of Na[B₁₁H₁₄] with NaH/NaHMDS (sodium bis(trimethylsilyl)amide), CF₃SiMe₃ in THF and K[B₁₁H₁₄] with KH, CF₃SiMe₃ in DME. This method avoids the exchange of cation and significantly simplifies the reaction setup, thus enabling convenient large-scale synthesis. It is believed that this method will support further application of Na[CB₁₁H₁₂] and K[CB₁₁H₁₂] as solid electrolytes for an all-solid-state battery.