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Semantic segmentation and hyperspectral unmixing are two central problems in spectral image analysis. The former assigns each pixel a discrete label corresponding to its material class, whereas the latter estimates pure material spectra, called endmembers, and, for each pixel, a vector representing material abundances in the observed scene. Despite their complementarity, these two problems are usually addressed independently. This paper aims to bridge these two lines of work by formally showing that, under the linear mixing model, pixel classification by dominant materials induces polyhedral-cone regions in the spectral space. We leverage this fundamental property to propose a direct segmentation-to-unmixing pipeline that performs blind hyperspectral unmixing from any semantic segmentation by constructing a polyhedral-cone partition of the space that best fits the labeled pixels. Signed distances from pixels to the estimated regions are then computed, linearly transformed via a change of basis in the distance space, and projected onto the probability simplex, yielding an initial abundance estimate. This estimate is used to extract endmembers and recover final abundances via matrix pseudo-inversion. Because the segmentation method can be freely chosen, the user gains explicit control over the unmixing process, while the rest of the pipeline remains essentially deterministic and lightweight. Beyond improving interpretability, experiments on three real datasets demonstrate the effectiveness of the proposed approach when associated with appropriate clustering algorithms, and show consistent improvements over recent deep and non-deep state-of-the-art methods. The code is available at: https://github.com/antoine-bottenmuller/polyhedral-unmixing