A fluorous, cyclative-capture strategy, based on a connective Pummerer-type process, has been developed for the rapid, one-pot construction of fluorous-tagged, heterocyclic frameworks. The process involves addition of a fluorous thiol, which triggers a Pummerer-type cyclisation resulting in the preparation of an N-heterocycle, the introduction of a fluorous tag and the construction of a sulfur linker. The fluorous tag then allows convenient purification of the tagged product from non-fluorous by-products through the use of Fluorous Solid Phase Extraction (FSPE)