Ceramic materials modified by hybrid MgO/carbon nanofibers systems are synthesized and characterized. Disordered carbon nanofibers were obtained via catalytic chemical vapor deposition of ethylene over nickel nanoparticles supported on the starting porous ceramic substrate. The carbon nanofibers were functionalized by acid treatment to increase the number of carbonyl and carboxyl groups on their surface. The hybrid samples were prepared by a deep coating method using Mg (OH)2 nanoparticles. After calcination, the obtained hybrid system attained a specific surface area of 242 m2·g−1 and a pore volume of 0.8 cm3·g−1. The hybrid material shows significantly enhanced sorption capacity towards carbon dioxide (4.9 mmol·g−1 CO2 uptake) under 367 K and 1 bar partial pressure of CO2.