Agricultural expansion into tropical and subtropical forests often leads to major social-ecological trade-offs. Yet, despite ever-more detailed information on where deforestation occurs, how agriculture expands into forests remains unclear. Here, we developed and mapped a novel set of metrics that quantify agricultural frontier processes at unprecedented spatial and temporal detail. Specifically, we first derived consistent time series of land-use/cover to, second, describe archetypical patterns of frontier expansion, pertaining to the speed, the diffusion and activity of deforestation, as well as post-deforestation land use. We exemplify this approach for understanding agricultural frontier expansion across the entire South American Chaco (1.1 million km2), a global deforestation hotspot. Our study provides three major insights. First, agricultural expansion has been rampant in the Chaco, with more than 19.3 million ha of woodlands converted between 1985 and 2020, including a surge in deforestation after 2019. Second, land-use trajectories connected to frontier processes have changed in major ways over the 35-year study period we studied. For instance, while ranching expansion drove most of the deforestation in the 1980s and 1990s, cropland expansion dominated during the mid-2000s in Argentina, but not in Paraguay. Similarly, 40% of all areas deforested were initially used for ranching, but later on converted to cropping. Accounting for post-deforestation land-use change is thus needed to properly attribute deforestation and associated environmental impacts, such as carbon emissions or biodiversity loss, to commodities. Finally, we identified major, recurrent frontier types that may be a useful spatial template for land governance to match policies to specific frontier situations. Collectively, our study reveals the diversity of frontier processes and how frontier metrics can capture and structure this diversity for guiding spatially targeted policies, and for uncovering high-level patterns of human-nature interactions.