Differentiating chemical and thermal expansion is virtually impossible to achieve experimentally. While thermal expansion stems from a softening of the phonon spectra, chemical expansion depends on the chemical composition of the material. In the present contribution, we, for the first time, completely decouple thermal and chemical expansion through first principles phonon calculations on BaCeO3, providing new fundamental insights to lattice expansion. We assess the influence of defects on thermal expansion, and how this in turn affects the interpretation of chemical expansion and defect thermodynamics. The calculations reveal that the linear thermal expansion coefficient is lowered by the introduction of oxygen vacancies being 10.6 × 10-6 K-1 at 300 K relative to 12.2 × 10-6 K-1 for both the protonated and defect-free bulk lattice. We further demonstrate that the chemical expansion coefficient upon hydration varies with temperature, ranging from 0.070 to 0.115 per mole oxygen vacancy. Ultimately, we find that, due to differences in the thermal expansion coefficients under dry and wet conditions, the chemical expansion coefficients determined experimentally are grossly underestimated - around 55% lower in the case of 10 mol% acceptor doped BaCeO3. Lastly, we evaluate the effect of these volume changes on the vibrational thermodynamics.