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The evolution of real-time stress in porous silicon (PS) during drying is investigated using micro-Raman spectroscopy. The results show that the PS sample underwent non-negligible stress when immersed in liquid and suffered a stress impulsion during drying. Such nonlinear transformation and nonhomogeneneous distribution of stress are regarded as the coupling effects of several physical phenomena attributable to the intricate topological structure of PS. The effect of dynamic capillarity can induce microcracks and even collapse in PS structures during manufacture and storage.