1. Stream ecosystem metabolism integrates production and respiration of organic matter and plays a fundamental role in the global carbon (C) cycle. Several studies have identified distal and proximal physical controls, for example, land use and transient storage, or the effects of water chemistry, that is, organic matter and nutrient availability, on stream metabolism. In parallel, research on organic matter quality has identified conspicuous gradients of chemical composition, yet mostly without demonstrating any functional implications. 2. We hypothesise that organic matter holds a key position in a more comprehensive causal framework of stream ecosystem metabolism, and that a concurrent study can improve mechanistic understanding. Specifically, we here postulate that dissolved organic matter (DOM) quality, that is, its chemical composition, acts as a control of ecosystem respiration (ER) as much as it is a result of gross primary production (GPP). As such, DOM quality likely forms a central link between land use and stream metabolism, besides known physical controls including transient storage and light availability. 3. To examine these hypotheses, we studied 33 streams in north-eastern Austria, a region with diverse land use ranging from semi-natural, forested areas to agricultural areas and settlements. We analysed DOM composition by absorbance and fluorescence spectroscopy, including modelling excitation–emission matrices with parallel factor analysis. We then opposed these data to GPP and ER estimated by fitting a metabolism model to single-station diurnal oxygen records. 4. Structural equation modelling revealed land use as a control on light conditions, DOM composition and concentration and nutrient concentrations, which together ultimately shaped GPP and ER. In particular, humified, coloured and aromatic DOM of predominantly terrestrial origin was prevalent in coniferous forest catchments and increased stream ER. Agricultural and urban areas enriched streams with phosphorous and nitrogen, which increased ER and GPP. Besides nutrients, GPP seemed to be weakly correlated with light availability and – in contrast to our hypothesis – left only a weak imprint on DOM composition. 5. Land-use change is rated as the most pervasive human influence on natural ecosystems and our results highlight its impact on aquatic GPP and ER in streams. To understand the role of inland waters in the global C cycle will require mechanistic understanding of ecosystem metabolism, which notably includes organic matter quality as a hitherto underappreciated key player.