In our research work we focused on novel labeling methods using (3+2) cycloadditions. Our main goal was to synthesize radiofluorinated 1,3-dipoles, which easily react with double and triple bonds. A second aim was to develop a simple method for the preparation of radiolabeled β-lactams. Furthermore 1,2-didehydrobenzene was used in association with the novel 1,3-dipoles to produce 18F-labeled homo- and heterocycles, which are difficult to prepare via conventional procedures. These approaches extend the spectrum of accessible radiolabeled probes and enable access to novel intelligent PET probes.