Pro-environmental decisions, such as rejecting pesticide use in agriculture, may stem from both environmental and health concerns. Identifying which concerns are more decisive for pro-environmental decisions, and whether this varies between people, depending on their value orientations, could offer valuable insights into how to best promote pro-environmental decisions across different audiences. While biospheric values likely underlie environmental concerns, it is unclear which value orientation underlies health concerns. In a preregistered online experiment (N = 823), we explored whether egoistic or personal safety values—a subtype of personal security values developed for this study—underlie health concerns regarding pesticide use in agriculture. Participants reported on their opposition to the use of a fictitious fungicide in potato cultivation, based on information about its risks to human health (relevant for egoistic and personal safety values) and/or the environment (relevant for biospheric values). Stronger biospheric values were consistently associated with stronger opposition to the fungicide’s use, regardless of the risk information. Egoistic values interacted with risk information, but these interactions contradicted our assumption that egoistic values reflect health concerns. Personal safety values showed no interaction with risk information and were not independently associated to opposition to the fungicide’s use. Our findings suggest that neither egoistic nor personal safety values serve as the basis for health concerns driving pro-environmental decisions. This underscores the need to identify an additional value orientation that reflects health concerns and develop measures to assess it.