Payments for Ecosystem Services (PES) initiatives, which provide financial incentives for management practices thought to increase the production of environmental benefits, have expanded across the global South since the late 1990s. These initiatives have thus far been conceptualized rather narrowly; by their early proponents as a novel economic instrument for more ‘rational’, effective and efficient environmental policy or by their critics as an exogenously imposed conduit of hegemonic neoliberalism. This introductory article to the special issue that follows advocates for and demonstrates a more grounded and historically situated approach for understanding the conformation and outcomes of PES in actual practice. It proposes a framework for examining individual PES initiatives as shaped by dynamic interactions between imposed structure and the development pathways and situated agency of actors in the territories in which they are implemented. It finds that certain ubiquitous components of this approach — the valuation of nature, the creation of institutions and the negotiations that inevitably surround the distribution of benefits — provide potential openings for articulation and engagement that can allow these initiatives to be contested, adapted, hybridized or more fully co-opted and captured. This framework opens a pathway for more inclusive, nuanced and grounded research on PES and on market-based environment and development policies more broadly.