This study investigates the thermal conductivity of unsaturated kaolin soil amended with biochar to promote sustainable geotechnical engineering. Biochar from agricultural waste offers the dual benefits of carbon sequestration and sustainable waste management. Experimental measurements were conducted for kaolin soil with 0% (control) and 10% biochar under varying moisture contents. Peach pit biochar increased thermal conductivity by 2–3% at 30–40% saturation and 40–50% at higher saturation as compared to the bare soil. Reed biochar decreased thermal conductivity by 1–2% at lower saturation but increased it by 55–60% at higher saturation. Applewood biochar increased thermal conductivity by 35–50% at moderate saturation, decreased beyond 50% water content, and had minimal variation at lower saturation. Further, the existing empirical models (such as Kersten and the Johansen model, Wiener’s model, and Mickley’s model) for predicting the thermal conductivity of materials were validated using the measured results of biochar-amended soils. Adding 10% biochar reduces thermal conductivity by 34.8%, and the Haigh model (2012) fits best with high accuracy and lower RMSE values than models such as Kersten and Johansen, which appears to be less reliable in case of biochar-amended soils. With an addition of biochar, the R2 values of the models decreased from a range of 0.8 to 0.9 to a range of 0.4–0.6, indicating the need for better model adaptation. Wiener bounds accurately predicted thermal conductivity at low saturation levels but varied greatly at higher ones. The most variable sample was peach pit biochar, highlighting the need to refine predictive models for material-specific differences. These findings provide a foundation for developing improved predictive models and integrating biochar into sustainable geotechnical and geothermal systems.