Extreme temperatures have increased in intensity, duration and frequency in the last century, with potential consequences on key ecological processes such as organic matter breakdown. Many stream ecosystems are fueled by the breakdown of terrestrial leaf litter, which is exposed to atmospheric conditions for certain periods of time before entering the stream. Thus, extreme warming or freezing events may affect the litter physicochemical structure, which could translate into altered breakdown within the stream. The above prediction was tested by exposing litter of common riparian tree species in southern Chile to freezing (−20 oC; dry or wet litter) or heating (40 oC) and comparing breakdown with control litter exposed to room temperature (20 oC), separating the effects of different breakdown agents (i.e., leaching, microorganisms and detritivores). The greatest effects were found in wet litter subjected to freezing; this treatment significantly increased leaching in the short term (48 h) and slowed down breakdown in the long term (30 days), mostly due to the inhibition of microbial breakdown. Heating also retarded microbial breakdown, but the effect was smaller. Our results suggest that short-term extreme temperatures—particularly cold ones—have the potential to slow down litter breakdown in streams, which will most likely impact global biogeochemical cycles where streams play a key role.