Pedotransfer functions (PTFs) are widely used in science and engineering to calculate soil thermal diffusivity (κ) as a function of soil moisture content and other soil physical properties. However, available data on κ are rather scarce and already developed PTFs suffer from significant uncertainties in applicability and performance. Few studies attempted to systematically review and evaluate these PTFs with large dataset of κ. The objectives of this study were to (1) review and collate currently available PTFs for κ; (2) compile a κ dataset to evaluate performance of these PTFs, (3) build a machine learning (ML) (i.e., random forest-RF) model with three classes of soil physical properties to determine soil physical properties most appropriate to use as predictors for calculating κ, and (4) compare the RF modelling with the traditional PTFs. The correlation coefficient (r), centered root-mean-square (E'), and standard deviation (SD) were used to evaluate the performance of the above PTFs. A total of nine PTFs were synthesized and assessed with a compiled dataset consisting of 998 measurements from 106 soils with a wide range of textures. In general, the PTFs of Lukiashchenko and Arkhangelskaya (2018) (LA2018–1 and LA2018–2) perform the best. While the quadratic equation of Mady and Shein (2018) (MS2018–1 and MS2018–2) showed better performance for coarse and medium textured soil. However, the overall performance of the nine PTFs for predicting κ was not as accurate as RF. RF can satisfactorily calculate κ taking into account sand, silt, clay contents, and soil moisture content as predictors.