In this paper, a novel approach where irradiated fuel thermochemistry and gas release are coupled is presented in details and illustrated by the simulations of some tests of the VERCORS program characterized by increasing temperatures and varying gas composition in the furnace (oxidizing or reducing conditions). At each step of the tests, the oxidation/reduction of the nuclear fuel and the fission product chemical speciation are precisely assessed thanks to a thermochemical equilibrium calculation relying on the OpenCalphad thermochemical solver and on a built-in thermochemical database derived from the SGTE database and completed by a solid solution model for the U-O-fission product system. Fission product releases are estimated from the chemically reactive gases that form in the fuel (according to the thermochemical calculation) and from a gas diffusion model based on the equivalent sphere model. The gas diffusion model takes into account not only the noble gases available in the fuel prior to the test but also the chemically reactive gases that form during the test. It is shown that the proposed coupled approach provides a consistent estimation of fission product release (I, Te, Cs, Mo, Ba) during the VERCORS tests in spite of the simple gas diffusion mechanism considered in the simulations (no distinction between the fission products). The proposed coupled approach is used to test some thermochemical hypotheses to improve the calculated release of some fission products (Ba, Mo).