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Abstract Disturbances can alter the structure and function of ecosystems. In stream ecosystems, changes in discharge and physicochemistry at short, intermediate, and long recurrence intervals can affect food webs and ecosystem processes. In this paper, we compare pH regimes in streams at La Selva Biological Station, Costa Rica, where episodic acidification frequency across the stream network varies widely due to buffering from inputs of bicarbonate‐rich interbasin groundwater. To examine the effects of acidification on ecosystem structure and function, we experimentally increased the buffering capacity of a headwater stream reach and compared it to an unbuffered upstream reach. We compared these reaches to a naturally buffered and unbuffered reaches of a second headwater stream. We quantified ecosystem structural (macroinvertebrate assemblages on leaf litter and coarse woody debris) and functional responses (leaf litter and coarse woody debris decomposition rates, and growth rates of a focal insect taxon [Diptera: Chironomidae]). Non‐metric multidimensional scaling and analysis of similarity revealed that macroinvertebrate assemblages were relatively homogenous across the four study reaches, although the naturally buffered reach was the most dissimilar. Ecosystem function, as measured by chironomid growth rates, was greater in the naturally buffered reach, while decomposition rates did not differ across the four reaches. Our results indicate that biological assemblages are adapted to pH regimes of frequently acidified stream reaches. Our experiment informs the effects on structure and function at short time scales in streams that experience moderate acidification, but larger magnitude acidification events in response to hydroclimatic change, as projected under climate change scenarios, may induce stronger responses in streams.