Abstract. Heterotrophic bacteria process nearly half of the organic matter produced by phytoplankton in the surface ocean. Much of this organic matter consists of high molecular weight (HMW) biopolymers such as polysaccharides and proteins, which must initially be hydrolyzed to smaller sizes by structurally specific extracellular enzymes. To assess the relationships between substrate structure and microbial community composition and function, we concurrently determined carbohydrate abundance and structural complexity, bacterial community composition, and peptidase and polysaccharide hydrolase activities throughout the water column at four distinct stations in the western North Atlantic Ocean. Although the monosaccharide constituents of particulate organic matter (POM) were similar among stations, the structural complexity of POM-derived polysaccharides varied by depth and station, as demonstrated by polysaccharide-specific antibody probing. Bacterial community composition and polysaccharide hydrolase activities also varied by depth and station, suggesting that the structure and function of bacterial communities—and the structural complexity of their target substrates—may be interrelated. Thus, the extent to which bacteria can transform organic matter in the ocean is dependent on both the structural complexity of the organic matter and their enzymatic capabilities in different depths and regions of the ocean.