Fluorinated asymmetric aryl ketones represent a pivotal class of organic synthesis intermediates, which have garnered widespread application in the realms of organic chemistry, materials science, and drug discovery. Herein, we report a pioneering nucleophilic aromatic substitution (S N Ar) reaction involving aryl aldehydes and polyfluoroarenes, elegantly catalyzed by N-heterocyclic carbene (NHC). This innovative strategy yields bis(hetero)aryl ketone products in yields ranging from moderate to exceptional (40–83%), all achieved under gentle conditions, devoid of both transition metals and directing groups. The versatility of this method is underscored by its compatibility with a broad spectrum of substrates, particularly exhibiting remarkable resilience toward alkoxy functional groups. Notably, we have successfully transformed an array of biologically active molecules, crafting a series of their corresponding derivatives with precision.