In this work, three-dimensional (3D) C_f/SiBCN composites were fabricated by polymer infiltration and pyrolysis (PIP) with poly(methylvinyl)borosilazane as SiBCN precursor. The 3D microstructure evolution process of the composites was investigated by an advanced X-ray computed tomography (XCT). The effect of dicumyl peroxide (DCP) initiator addition on the crosslinking process, microstructure evolution, and mechanical properties of the composites were uncovered. With the addition of a DCP initiator, the liquid precursor can cross-linking to solid-state at 120 °C. Moreover, DCP addition decreases the release of small molecule gas during pyrolysis, leading to an improved ceramic yield 4.67 times higher than that without DCP addition. After 7 PIP cycles, density and open porosity of the final C_f/SiBCN composite with DCP addition are 1.73 g·cm⁻³ and ∼10%, respectively, which are 143.0% higher and 30.3% lower compared with the composites without DCP addition. As a result, the flexural strength and elastic modulus of C_f/SiBCN composites with DCP addition (371 MPa and 31 GPa) are 1.74 and 1.60 times higher than that without DCP addition (213 MPa and 19.4 GPa), respectively.