Aquatic insects are key to wetland ecological functioning, and the distribution of amphibious insects such as Odonata jointly depends on environmental conditions in the aquatic and terrestrial settings. Therefore, untangling the relative effects of within‐wetland and landscape composition can help predict the responses of Odonata to environmental alterations in wetlands. Using data from 19 wetlands spanning over the southern Brazilian Pampa (center‐western Rio Grande do Sul state), we assessed the relative importance of water chemistry and land‐cover variables to the richness and composition of larval Odonata assemblages (and suborders Anisoptera and Zygoptera). Anisoptera richness decreased with pH and bare soil area. Water pH and areas of bare soil, mosaic of agricultural land use, and waterbodies land cover were the main drivers of Odonata and Zygoptera composition. Our results indicate that land cover is the main driver of the assemblage structure of larval Odonata, although a complex interplay of mechanisms associated with land conversion and water quality drive the distribution of larval Odonata in freshwater wetlands of the Brazilian Pampa. The major implication of our findings is that land cover modification is the major threat to Odonata distribution in Pampean wetlands, with potential impacts on the trophic structure and functioning of these ecosystems.