Selective modification of biological systems via click reactions is an important method to study their properties and function under native conditions. One of the most used method is the strain-promoted azide-alkyne cycloaddition (SPAAC) reaction between azides and strained cyclooctynes. In this work, we show, that fluorination of the azide reagents enhances their click reactivity and enables achieving of excellent selectivity when used in combination with simple alkyl azides. This work extends the available toolkit for efficient and selective modification of (bio)molecules under benign, metal-free condition.