We have developed a broadly applicable and modular synthetic approach for fluoroalkyl-substituted cyclopropenes, utilizing fluoroalkylacylsilanes as carbynyl cation equivalents. The success of this reaction is attributed to the efficient photocatalytic fluoroalkyl siloxycarbene-mediated [2 + 1] cycloaddition with alkynes, followed by acid-catalyzed C–O bond functionalization, facilitated by the leaving group ability of the siloxyl group. The reactions exhibit a wide substrate scope, resulting in convenient access to diversified fluoroalkyl-substituted cyclopropenyl ethers, arenes, alkanes, thioethers, amines, and azides.