Straightforward radiosynthesis protocols for F-labeled radiopharmaceuticals are an indispensable but often overlooked prerequisite to successfully perform molecular imaging studies in vivo by PET. In recent years, thanks to the expansion of the F chemical toolbox, structurally diverse and novel clinically relevant radiopharmaceuticals have been synthesized with both high efficiency and ready implementation. This article provides an overview of recent F-labeling methodologies, specifically for B-F, Si-F, Al-F, and iodine (III)-mediated radiofluorination via the spirocyclic iodonium ylide technology.