This paper describes the preparation and post-functionalisation of a new polymeric support based on emulsion-derived foams and called polyHIPEs. The remaining pendant vinylic bonds are easily functionalised by a free radical mechanism. The large pores and channels of this material allow an easy access of the reagent in solution toward the grafted species. PolyHIPE-supported thiol, in the presence of an excess of triethylsilane, showed a good activity and selectivity toward reductive cyclisation of 6-bromohex-1-ene and 1-allyloxy-2-bromobenzene.