Pompilid spider wasps reproduce by stinging and paralyzing spider hosts whose immobilized bodies serve as food stores for developing wasp larvae. The family is extremely cosmopolitan and is found from tropical to temperate latitudes on all continents save Antarctica. They are also renowned for using some of the most extraordinarily painful venom of any insect as a defense against predators including humans. Their has been preliminary research into the venoms of these wasps, but it remains unclear what toxins or mechanisms underlie the long-term paralysis of their prey or the pain of their stings. Here we present the first comprehensive venomics of any pompilids using a combination of venom gland transcriptomics and venom proteomics from 4 genera as part of the first investigation of any Australian pompilid venoms. We discuss these findings as well as potential techniques for unlocking the evolutionary and biodiscovery potential of venomics from preserved specimens in natural history collections.