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An insightful understanding of the formation mechanism of process-inherent defects and deformation is increasingly important for the property evaluation and structural design of ceramic matrix composites (CMCs). For this purpose, a coupled thermal–diffusive–mechanical modeling approach was proposed by considering three important phenomena that occur during the pyrolysis process for manufacturing CMCs: variations of the physical and mechanical properties of the constituents, generation and diffusive of pyrolysis gas, and multiple thermal deformations. The synergistic effects of these three phenomena on the stress, damage development, microstructural morphology, and process deformation of SiC matrix composites were investigated using finite-element simulations. This new approach was validated by comparing the simulation and experimental results. Significant volume shrinkage of the matrix during the polymer-to-ceramic transformation resulted in large tensile stresses and subsequent highly fragmented microstructure in CMCs. The pyrolysis-gas-induced expansion on the matrix under a damage state may yield a positive process deformation of CMCs at the macroscale, overcoming the effects of the volume shrinkage of the bulk matrix at the microscale. The modeling approach is expected to guide high-quality manufacturing of CMCs and comprehensive studies of structure–processing–property relationships.