Contact between contaminated hands and the mouth or the area around the mouth (the perioral area) can result in inadvertent ingestion exposure. Exposure by this route is known to occur among children, but adults may also be exposed. Observations of 48 workers were carried out in 8 UK worksites to study hand- and object-to-mouth behavior. Each subject was observed in real-time for ~60 min during normal work activities. Each contact was recorded along with information about time of contact, glove use, respirator use, task and object type. Subjects were interviewed to gather information about smoking, nail biting and risk perception. The effects of factors (glove use, respirator use, smoking, nail biting, risk perception, work sector and task group) on contact frequency were assessed using non-parametric tests and Poisson regression models. Several determinants of contact frequency were identified, including time spent “between” work tasks, glove and respirator use, smoking and nail biting. Hand-to-mouth contact frequencies were particularly high while workers were “between” work tasks (23.6 contacts per hour, compared with the average contact frequency of 6.3 per hour). The factors that were related to contact frequency differed between object- and hand-to-mouth contacts, suggesting that these should be considered separately. These findings could be used for developing exposure models, to inform measurements of inadvertent ingestion among adults and to identify control strategies.