Biogenic amines modulate a range of social behaviours, including sociability and mechanisms of group cohesion, in both vertebrates and invertebrates. Here, we tested if the biogenic amines modulate honey bee (Apis mellifera) sociability and nestmate affiliation. We examined the consequences of treatments with biogenic amines, agonists and antagonists on a bee's approach to, and subsequent social interactions with, conspecifics in both naturally hive-reared bees and isolated bees. We used two different treatment methods. Bees were first treated topically with compounds dissolved in the solvent dimethylformamide (dMF) applied to the dorsal thorax, but dMF had a significant effect on the locomotion and behaviour of the bees during the behavioural test that interfered with their social responses. Our second method used microinjection to deliver biogenic amines to the head capsule via the ocellar tract. Microinjection of dopamine and a dopamine antagonist had a strong effect on bee sociability, likelihood of interaction with bees, and nestmate affiliation. Octopamine treatment blocked social interaction with other bees, and serotonin increased the likelihood of social interactions. HPLC measurements showed that isolation reduced brain levels of biogenic amines compared to hive-reared bees. Our findings suggest that dopamine is an important neurochemical component of social motivation in bees. This finding advances a comparative understanding of the processes of social evolution.