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Diffusion models have recently motivated great success in many generation tasks like object removal. Nevertheless, existing image decomposition methods struggle to disentangle semi-transparent or transparent layer occlusions due to mask prior dependencies, static object assumptions, and the lack of datasets. In this paper, we delve into a novel task: Layer-Wise Decomposition of Alpha-Composited Images, aiming to recover constituent layers from single overlapped images under the condition of semi-transparent/transparent alpha layer non-linear occlusion. To address challenges in layer ambiguity, generalization, and data scarcity, we first introduce AlphaBlend, the first large-scale and high-quality dataset for transparent and semi-transparent layer decomposition, containing six subtasks with different characteristics (e.g., translucent flare removal, semi-transparent cell decomposition, glassware decomposition). Building on this dataset, we present DiffDecompose, a diffusion Transformer-based framework that learns the posterior over possible layer decompositions conditioned on the input image, semantic prompts, and blending type. Rather than regressing alpha mattes directly, DiffDecompose performs In-Context Decomposition, enabling the model to predict one or multiple layers without per-layer supervision, and introduces Layer Position Encoding Cloning to maintain pixel-level correspondence across layers. Extensive experiments on the proposed AlphaBlend dataset and public LOGO dataset verify the effectiveness of DiffDecompose. Code will be publicly available at https://github.com/Wangzt1121/DiffDecompose.