Several thermal protection systems employ sacrificial composite layer that undergoes thermo-chemical decomposition in high-temperature environment. This results in the pyrolysis gas formation (endothermic reaction) that gets trapped inside the voids generated in the ablative matrix phase. These trapped gases apply pore pressure on the structure, along with the mechanical loading, thus significantly influencing the structure failure. A novel thermo-chemical (TC) decomposition and thermo-mechanical (TM) deformation-based coupled multi-physics formulation, applicable to ablative composite systems, is thus presented. A novel shrinkage expression, due to ablative matrix decomposition, is derived. The TC + TM coupled formulation is converted to stress update process, and its results are validated against the available experimental data. The proposed formulation is also converted to boundary value problem employing non-linear finite element framework (NL-FEM). The Jacobian matrices, for one- and two-dimensional cases, are systematically derived, and the proposed NL-FEM formulation is successfully verified against several benchmark problems.The transient heat conduction equation is finally coupled with the proposed TC + TM formulation (one-way coupling) thus enabling the analysis of more realistic situations where the constant heating rate assumption is not valid. The coupled formulation is finally implemented for several test cases and it is demonstrated that, it has a significant influence on pore pressure and porosity evolution (through pore volumetric strain) within the ablative matrix phase.