Primary tropical forests provide crucial environmental services, including carbon storage and hydrological regulation. Options for promoting forest conservation include payments for environmental services (PES) programmes that provide financial incentives to local actors, in exchange for reduced forest clearance. The success of voluntary PES (defined in terms of avoided primary forest conversion) is contingent upon behavioural changes in enrolled actors. As both the degree of enrolment and likelihood of sustained behavioural change depend upon how PES compensation structures interact with existing actor economies, local heterogeneity in livelihood strategies may play a strong role in the ultimate success of PES programmes, particularly when compensation is not differentiated with respect to opportunity costs. We examined the influence of livelihood heterogeneity on the potential success of a deforestation-reduction PES with an undifferentiated reward structure. We collected socioeconomic and demographic data at the household and community levels across two large Amazonian extractive reserves where a spatially extensive PES programme (Bolsa Floresta) operates. We show that demographic and socioeconomic status varies widely across households and communities, and found that both households and communities that are most and least likely to convert primary forest receive similar financial incentives. Those households most engaged in manioc agriculture (the primary driver of local primary forest conversion) both benefitted from the highest annual incomes and incurred the greatest opportunity costs. We show that avoided primary forest conversion could be greatly increased with differentiated payment structures adjusted for local differences in opportunity costs and livelihood strategies, and present two metrics that could help to achieve that goal.