Mesoporous carbons (MPCs) with a bimodal distribution of pore diameters are more advantageous than their monomodal counterparts for applications in adsorption, catalysis, and drug delivery systems; however, reports on their fabrication remain limited. In this study, we successfully fabricated bimodal MPCs using a soft template method with poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA)-b-poly(4-vinylpyridine) (P4VP)-b-polystyrene (PS) and resol. The blend samples formed microphase-separated structures comprising PTFEMA spheres, PS cylinders, and matrix domains composed of P4VP and resol, leading to the separation of the PTFEMA and PS domains. The P4VP and resol matrix domains were carbonized at a high temperature of 900 °C, whereas the PTFEMA and PS domains were thermally decomposed. This process resulted in bimodal MPCs with both spherical and cylindrical mesopores. The pore diameters calculated using scanning electron microscopy were approximately 10 and 30 nm, while nitrogen adsorption measurements indicated a large specific surface area with a bimodal pore distribution.