Photodegradation of aboveground senescent plant material (plant litter) due to exposure to solar radiation has been identified as a dominant control on carbon (C) loss in semi-arid ecosystems , upturning traditional models of C cycling based only on available moisture and litter quality. In addition to the photochemical mineralization of organic matter [1, 2], sunlight alters the chemistry of cell walls in plant litter [3, 4], making them more susceptible to subsequent biotic degradation [5-7]. Nevertheless, the interactive effects of sunlight exposure, climate seasonality, and biotic decomposition on C turnover remain unresolved in terrestrial ecosystems. We show here that exposure to sunlight accelerated litter decomposition in a Patagonian woodland with a marked dry summer season. Controls on initial decomposition varied seasonally from direct photochemical mineralization in the dry summer to biotic degradation in the wet winter. By manipulating sunlight received by plant litter using spectral filters that attenuated ultraviolet and short-wave visible light, we demonstrate that direct photodegradation and its legacy, associated with increased microbial access to labile carbohydrates, are responsible for the acceleration of aboveground C turnover in this Mediterranean-type climate. Across plant species and over a 2-year period, litter exposed to the full solar spectrum decomposed twice as fast as litter that received attenuated sunlight. Changes in vegetation cover or biodiversity due to projected increased drought and dry season length  will likely exacerbate C losses from aboveground litter due to sunlight exposure, negatively impacting the C balance in ecosystems that are particularly vulnerable to global change .