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Ionic liquids [Bmim]BF4 and [Bpy]BF4 were employed as environmentally benign media in Doebner condensation to synthesize α,β-unsaturated carboxylic acid. The good results showed that [Bmim]BF4 and [Bpy]BF4 were efficient media for Doebner condensation, which could be recycled easily. The highest yields could reach 93% and 90% in [Bmim]BF4 and [Bpy]BF4, respectively.