SummaryThe first step in carbon (C) turnover, where senesced plant biomass is converted through various pathways into compounds that are released to the atmosphere or incorporated into the soil, is termed litter decomposition. This review is focused on recent advances of how solar radiation can affect this important process in terrestrial ecosystems. We explore the photochemical degradation of plant litter and its consequences for biotic decomposition and C cycling. The ubiquitous presence of lignin in plant tissues poses an important challenge for enzymatic litter decomposition due to its biological recalcitrance, creating a substantial bottleneck for decomposer organisms. The recognition that lignin is also photolabile and can be rapidly altered by natural doses of sunlight to increase access to cell wall carbohydrates and even bolster the activity of cell wall degrading enzymes highlights a novel role for lignin in modulating rates of litter decomposition. Lignin represents a key functional connector between photochemistry and biochemistry with important consequences for our understanding of how sunlight exposure may affect litter decomposition in a wide range of terrestrial ecosystems. A mechanistic understanding of how sunlight controls litter decomposition and C turnover can help inform management and other decisions related to mitigating human impact on the planet.