Ordered mesoporous carbons (OMCs), obtained by nanocasting using ordered mesoporous silicas (OMSs) as hard templates, exhibit unique arrangements of ordered regular nanopore/nanowire mesostructures. Here, we used nanocasting combined with hot-pressing to prepare 10 wt% OMC/OMS/SiO2 ternary composites possessing various carbon mesostructure configurations of different dimensionalities (1D isolated CS41 carbon nanowires, 2D hexagonal CMK-3 carbon, and 3D cubic CMK-1 carbon). The electric/dielectric properties and electromagnetic interference (EMI) shielding efficiency (SE) of the composites were influenced by spatial configurations of carbon networks. The complex permittivity and the EMI SE of the composites in the X-band frequency range decreased for the carbon mesostructures in the following order: CMK-3-filled > CMK-1-filled > CS41-filled. Our study provides technical directions for designing and preparing high-performance EMI shielding materials. Our OMC-based silica composites can be used for EMI shielding, especially in high-temperature or corrosive environments, owing to the high stability of the OMC/OMS fillers and the SiO2 matrix. Related shielding mechanisms are also discussed.