In this study we present a comprehensive thermodynamic description of the binary CsF-ThF₄ system. The phase equilibria of several intermediate compositions in this system have been determined using the DSC technique combined with a post-analysis using powder X-ray diffraction. Considering all the novel experimental data, a thermodynamic model for the CsF-ThF₄ system has been developed for the first time using the Calphad approach. The present model reproduces very well the measurements performed. Knudsen effusion mass spectrometry (KEMS) has further been used to investigate the vapour pressure over the molten CsF-ThF₄ salt and to determine the thermodynamic activities of CsF and ThF₄ in the liquid solution. As part of this study, the vaporization of pure CsF was examined and the results were compared with the literature showing a good agreement. Next, the vapour pressure of CsF-ThF₄ in the liquid solution was investigated by measuring three samples with compositions X ThF₄ = (0.4, 0.6, 0.8) mol/mol. A strong negative deviation from Raoult's law was observed for both species, more evident in case of CsF, and a good agreement with the predictions of our thermodynamic model was found. This article is a pre-requisite for the assessment of the ternary LiF-CsF-ThF₄ system.