The thermoelastic behavior of the porous carbon/phenolic composites is studied using the thermomechanical response model of chemically decomposing composites. The model includes thermal dependence of the porous composites, porosity in the pyrolysis process, pore pressure due to decomposing gases, and shrinkage. The poroelastic coefficients are calculated based on representative volume element model and finite element analysis. The internal stress distribution caused by pores and pore pressure, and the overall deformation are verified. The effects of the poroelastic coefficients on the thermoelastic behavior are examined through numerical experiments.