A suite of exoenzyme activities was assayed in three New Zealand streams draining pasture, native forest, and a pine catchment. There were differences among catchments in activity of three of the five enzymes assayed (cello‐biohydrolase, N‐acetylglucosaminidase, and dihydroxylphenylalanine oxidation). A principal components analysis (PCA) demonstrates that patterns of enzyme activity can be used to separate the three stream types. An experimental addition of algal‐leachate, leaf‐litter leachate, and high dissolved organic carbon (DOC) water from a small seep also resulted in marked shifts in epilithic enzyme activities 1 day after DOC additions. Oxidative enzymes showed a particularly strong response to additions of humic DOC. As for the field samples, a PCA showed large differences among treatments indicating that exoenzyme patterns can be used to examine which DOC sources predominate in different streams. Application of this approach to describing differences among streams will require detailed seasonal sampling together with longer‐term experiments.