Biodiversity–ecosystem functioning and food-web complexity–stability relationships are central to ecology. However, they remain largely untested in natural contexts. Here, we estimated the links among environmental conditions, richness, food-web structure, annual biomass and its temporal stability using a standardised monitoring dataset of 99 stream fish communities spanning from 1995 to 2018. We first revealed that both richness and average trophic level are positively related to annual biomass, with effects of similar strength. Second, we found that community stability is fostered by mean trophic level, while contrary to expectation, it is decreased by species richness. Finally, we found that environmental conditions affect both biomass and its stability mainly via effects on richness and network structure. Strikingly, the effect of species richness on community stability was mediated by population stability rather than synchrony, which contrasts with results from single trophic communities. We discuss the hypothesis that it could be a characteristic of multi-trophic communities.