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Cross-modal knowledge distillation (CMKD) studies how a (large) teacher model trained on one type of data (e.g., images) can guide a (smaller) student model building on another type of data (e.g., text/audio). Existing CMKD methods often require paired multi-modal data with aligned semantics, but obtaining such paired data are often costly and impractical. To mitigate this limitation, we develop a new CMKD framework for the more challenging setting where paired data are unavailable. In particular, we establish a cross-modal distributional relationship between teacher and student models, which reveals two fundamental quantities governing effective distillation: feature alignment and label alignment. These quantities characterize semantic discrepancy between modalities at the levels of representation and prediction distributions, respectively. Motivated by this insight, we propose a principled framework, with theoretical guarantees, that enables effective cross-modal knowledge distillation by aligning distributions rather than individual samples. Extensive experiments across a wide range of multimodal benchmarks show that our framework is highly effective in both unpaired and paired data settings, improving significantly over prior work.