A transition metal-free strategy is reported for the site-selective O-arylation of cyclic 1,3-dicarbonyls with polyfluoroarenes. This method offers a straightforward and alternative pathway for the synthesis of aryl ethers, accommodating a wide array of functional groups. Furthermore, the practical value of this methodology is underscored by its facile scalability to gram-level reactions, its potential for diverse synthetic applications, and its aptitude for complex molecules modifications.