Herein, we report a transition-metal-free alkynylthiolation of tertiary α-carbonyl bromides with 1,2,3-thiadiazoles. Those reactions involve the in-situ generation of alkynylthiolate anions from 1,2,3-thiadiazoles in the presence of a base and then their halogenophilic nucleophilic substitution (SN2X) reactions. The exceptionally mild reaction conditions, broad substrate scope, and excellent functional group tolerance highlight the utility of this method to prepare privileged motifs from readily available 1,2,3-thiadiazoles and tertiary α-carbonyl bromides feedstocks. Gram-scale reaction and diverse synthetic transformations convincingly demonstrate the synthetic potential of this method.