Rising temperatures in the Arctic have led to the thawing of tundra soils, which is rapidly changing terrain, hydrology, and plant and microbial communities, causing hotspots of biogeochemical activity across the landscape. Despite this, little is known about how nutrient-rich low molecular weight dissolved organic matter (LMW DOM) varies within and across tundra ecosystems. Using a high-resolution nano-liquid chromatography-mass spectrometry (LC/MS) approach, we characterized the composition and availability of LMW DOM from high-centered polygons (HCP) and low-centered polygons (LCP) with Eriophorum angustifolium or Carex aquatilis as the dominant vegetation. Over 3000 unique features (i.e., discrete mass/charge ions) were detected; 521 were identified as differentially abundant between polygonal types and 217 were putatively annotated using high mass accuracy MS data. While polygon type was a strong predictor of LMW DOM composition and availability, vegetation and soil depth were also important drivers. Extensive evidence was found for enhanced microbial processing at the LCP sites, which were dominated by Carex plant species. We detected significant differences between polygon types with varying aboveground landscape features or properties, and hotspots of biogeochemical activity, indicating LMW DOM, as quantified by untargeted exometabolomics, provides a window into the dynamic complex interactions between landscape topography, vegetation, and organic matter cycling in Arctic polygonal tundra soils.