Results from several long‐term monitoring programs in the western Adirondack Mountains, New York, indicate that acid–base chemistry of headwater streams has remained unchanged or improved only marginally since the 1990s. A paucity of quantitative fishery data, however, limits our understanding of the pre‐acidified communities as well as present‐day impacts of acidification on fish assemblages, which impedes efforts to evaluate temporal trends and biological recovery in streams of the region. Fish communities were characterized at 48 streams (chemistry was assessed at 47 streams) in the western Adirondacks at least once during summer 2014–2016 to assess present‐day effects of acidification on fish assemblages, refine important relations, and identify biological targets and chemical effect thresholds that could help gauge biological recovery across the region. Concentrations of inorganic aluminum (Al_i) exceeded chronic and acute toxicity thresholds (1.0 and 2.0 μmol/L) in 21.3% and 8.5%, respectively, of 47 study streams sampled during summer 2014–2016 and in 64.0% and 44.0% of 25 streams sampled during spring 2014–2015. In streams with summer Al_iconcentrations less than 1.0 μmol/L, community richness, density, and biomass averaged 2.0 species, 444.2 fish/0.1 ha, and 1,924.4 g/0.1 ha, respectively, whereas density and biomass of Brook Trout Salvelinus fontinalis populations averaged 280.8 fish/0.1 ha and 1,384.0 g/0.1 ha, respectively. These findings identify defensible targets for biological recovery and show that Al_i toxicity is not a major concern for fish assemblages in most streams during summer base flow periods but is potentially a serious issue for fish in as many as two‐thirds of streams during spring high flows. Though additional data are needed to address several limitations and information gaps, results from this study provide a sound foundation to gauge biological recovery, detect future effects of climatic stressors, and help ensure that functional stream ecosystems can be sustained or restored in parts of the Adirondacks.