Fe doped ceramic foams (CFs) were synthesized by organic template replication and consequently modified by carbon nanotubes (CNTs) via facile chemical vapor deposition (CVD). CNTs were in situ anchored on the surface of CFs with excellent mechanical stability. The influence of CVD temperature on yield, diameter, and graphitization degree of as-prepared CNTs was thoroughly investigated. Pd nanoparticles were deposited onto CNT modified CFs (CNTs@CFs) forming a structured catalyst (Pd/CNTs@CFs) toward polystyrene (PS) hydrogenation. Pd/CNTs@CFs displayed a final hydrogenation degree of 52.7%, which was 5.1 times that of CF supported Pd catalyst (Pd/CFs) under the same reaction conditions. The outstanding catalytic activity of Pd/CNTs@CFs could be ascribed to the accessible effective Pd active sites with high dispersion and enhanced adsorption of PS chains onto the CNT surface confirmed by molecular dynamics simulation. It showed the promising industrial potential of CNTs@CFs as structured supports for different active components to eliminate catalyst filtration processes.