Polyhedral milliparticles (PMPs) have promising applications in self‐assembly, tissue engineering, mechanical engineering, and photonics. The shapes and sizes of the PMPs have great impact on their functions. To date, the reported methods for adjusting the shapes and sizes of PMPs are still limited. Especially, it remains a challenge to fabricate the PMPs with high asymmetry. Here, we present a facile and efficient approach that focuses on the alteration of the relative positions between the microchannel and the UV light to tailor the shaping process of the PMPs. By tuning the rotation angle and translation displacement, a variety of monodisperse PMPs with both centrosymmetric and noncentrosymmetrical structures are synthesized, including tetrahedra, pentahedra, hexahedra, and so forth. Moreover, the polymeric PMPs are loaded with silica nanoparticles and further sintered into silica. The obtained silica PMPs hold great potential for the applications such as machining tools, abrasives, and electronics.