The application of fluorous mixture synthesis (FMS) for accessing natural products and theirstereoisomers was validated by the total synthesis of all 16 stereoisomers of the pine sawfly sexpheromone. Four fluorous p-methoxybenzyl groups were used as tags, and a “4-mix-4-split” approachwas employed in a divergent synthesis. This paper presents the details of the FMS of pine sawflysex pheromones with an emphasis on identification and solving of problems encountered whenworking with fluorous mixtures.