Cross-modal garment synthesis and manipulation will significantly benefit the way fashion designers generate garments and modify their designs via flexible linguistic interfaces.Current approaches follow the general text-to-image paradigm and mine cross-modal relations via simple cross-attention modules, neglecting the structural correspondence between visual and textual representations in the fashion design domain. In this work, we instead introduce DiffCloth, a diffusion-based pipeline for cross-modal garment synthesis and manipulation, which empowers diffusion models with flexible compositionality in the fashion domain by structurally aligning the cross-modal semantics. Specifically, we formulate the part-level cross-modal alignment as a bipartite matching problem between the linguistic Attribute-Phrases (AP) and the visual garment parts which are obtained via constituency parsing and semantic segmentation, respectively. To mitigate the issue of attribute confusion, we further propose a semantic-bundled cross-attention to preserve the spatial structure similarities between the attention maps of attribute adjectives and part nouns in each AP. Moreover, DiffCloth allows for manipulation of the generated results by simply replacing APs in the text prompts. The manipulation-irrelevant regions are recognized by blended masks obtained from the bundled attention maps of the APs and kept unchanged. Extensive experiments on the CM-Fashion benchmark demonstrate that DiffCloth both yields state-of-the-art garment synthesis results by leveraging the inherent structural information and supports flexible manipulation with region consistency.