An alternative strategy for the mechanochemical defluorinative acylation of ortho-hydroxyarylenaminones has been developed to synthesise 3-acylchromones utilizing CF3-compounds via activation of the C−F bound of the trifluoromethyl group in the presence of ytterbia (Yb2O3). The current protocol tolerated a wide range of coupling substrates to access a library of diversely substituted 3-acylchromones under the mechanochemically induced domino cyclisation mode. This is the first report for the deflourinative transformation of the inert CF3 group to the corresponding carbonyl functionality under the mechanochemical conditions.