Objective. Conventional computed tomography (CT) imaging does not provide quantitative information on local thermal changes during percutaneous ablative therapy of cancerous and benign tumors, aside from few qualitative, visual cues. In this study, we have investigated changes in CT signal across a wide range of temperatures and two physical phases for two different tissue mimicking materials, each. Approach. A series of experiments were conducted using an anthropomorphic phantom filled with water-based gel and olive oil, respectively. Multiple, clinically used ablation devices were applied to locally cool or heat the phantom material and were arranged in a configuration that produced thermal changes in regions with inconsequential amounts of metal artifact. Eight fiber optic thermal sensors were positioned in the region absent of metal artifact and were used to record local temperatures throughout the experiments. A spectral CT scanner was used to periodically acquire and generate electron density weighted images. Average electron density weighted values in 1 mm3 volumes of interest near the temperature sensors were computed and these data were then used to calculate thermal volumetric expansion coefficients for each material and phase. Main results. The experimentally determined expansion coefficients well-matched existing published values and variations with temperature—maximally differing by 5% of the known value. As a proof of concept, a CT-generated temperature map was produced during a heating time point of the water-based gel phantom, demonstrating the capability to map changes in electron density weighted signal to temperature. Significance. This study has demonstrated that spectral CT can be used to estimate local temperature changes for different materials and phases across temperature ranges produced by thermal ablations.