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This article reports on the fabrication and subsequently on the thermal properties of a biomaterial filled polymer composite consisting of polyester and walnut shell powder (WSP) in different proportions. The focus has been given to the evaluation of effective properties of the composites like thermal conductivity, glass transition temperature, and coefficient of thermal expansion. The experimental findings obtained for thermal conductivity are supported by the mathematical and numerical analysis made under suitable assumptions. A mathematical correlation is proposed to predict the effective thermal conductivity (Keff) of such particulate filled polymer composites. For the numerical study, a commercially available finite‐element package ANSYS19.2R2 is used to calculate the thermal conductivity of the composites. One dimensional heat conduction analysis is performed across composites with the periodic and randomly oriented arrangement of spherical fillers in different concentrations. Thermal conductivities of the composites are measured with Unitherm Model 2022 tester to validate the results. These values are then compared with effective thermal conductivities obtained from the proposed mathematical correlation and are found to be in close agreement with one another. It is concluded from this study that the addition of WSP improves the thermal insulation capability of neat polyester to a reasonable extent.