Aculeata is an extremely diverse lineage of hymenopteran insects. The name, aculeate, is derived from the Latin word aculeus meaning stinger. This refers to the defining feature of the group, a weaponised ovipositor. This weaponised ovipositor is an aculeus that is able to inject complex cocktails of bioactive molecules into prey or predators. There are over 70, 000 described species and a wide diversity of life history traits, including parasitoids, predators and pollinivores. Aculeates can be further divided into two general categories; solitary and social. In general, the venoms of solitary insects are non-lethal and paralytic allowing for feeding on prey items. Contrastingly, the venom of social insects has lost its paralytic function and is generally used for defence. Research into the venom of aculeates has only been undertaken on a few medically important species, neglecting a large portion of the group. The primary aim of this thesis was to elucidate differences in the aculeate venom system as a result of social behaviour. This was accomplished by incorporating complementary approaches of scanning electron microscopy, energy dispersion spectroscopy, proteomics, transcriptomics, functional assays, and phylogenetics, providing a broad look into the complexities of the aculeate venom system. Chapter One reviews the aculeate venom system, tying together what is already known about the venom-delivery apparatus and venom composition across the group. The chapter highlights the lack of information describing venom components from solitary species and the absence of any major comparative analyses. Chapter Two provides the first insight into the morphological adaptations and metal accumulation of the aculeus in Aculeata. Chapter Three presents an in depth comparative description of the venom profiles of various solitary and social species, revealing striking differences the most likely correlate with venom use. The data explored in Chapter Four reveals the phylogenetic and evolutionary histories of the major allergen families found in hymenopteran venoms, demonstrating that most allergens are under the influence of strong negative selection. Overall this thesis provides a basis upon which to understand these understudied insect venom systems and will have wide-reaching effects pertaining to the evolution and ecology of stinging bees, wasps, and ants.