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SUMMARY: The photosynthetic capacity of mature leaves increases after several days' exposure to constant or intermittent episodes of high light (HL) and is manifested primarily as changes in chloroplast physiology. How this chloroplast‐level acclimation to HL is initiated and controlled is unknown. From expanded Arabidopsis leaves, we determined HL‐dependent changes in transcript abundance of 3844 genes in a 0–6 h time‐series transcriptomics experiment. It was hypothesized that among such genes were those that contribute to the initiation of HL acclimation. By focusing on differentially expressed transcription (co‐)factor genes and applying dynamic statistical modelling to the temporal transcriptomics data, a regulatory network of 47 predominantly photoreceptor‐regulated transcription (co‐)factor genes was inferred. The most connected gene in this network was B‐BOX DOMAIN CONTAINING PROTEIN32 (BBX32). Plants overexpressing BBX32 were strongly impaired in acclimation to HL and displayed perturbed expression of photosynthesis‐associated genes under LL and after exposure to HL. These observations led to demonstrating that as well as regulation of chloroplast‐level acclimation by BBX32, CRYPTOCHROME1, LONG HYPOCOTYL5, CONSTITUTIVELY PHOTOMORPHOGENIC1 and SUPPRESSOR OF PHYA‐105 are important. In addition, the BBX32‐centric gene regulatory network provides a view of the transcriptional control of acclimation in mature leaves distinct from other photoreceptor‐regulated processes, such as seedling photomorphogenesis. Significance Statement: Identifying genes that control plants' intrinsic photosynthetic capacity would provide opportunities for increasing crop productivity. Photosynthetic capacity in mature leaves increases after several days' exposure to episodes of high‐light intensity (HL), which is defined as HL acclimation. Using temporal transcriptomics data and dynamic modelling, we inferred a BBX32‐centric 47‐member Gene Regulatory Network, members of which control, in the first hours of HL exposure, cellular processes that result in enhanced photosynthetic capacity 5 days later. [ABSTRACT FROM AUTHOR]