Thermal inertia and albedo provide information on the distribution of surface materials on Mars. These parameters have been mapped globally on Mars by the Thermal Emission Spectrometer (TES) onboard the Mars Global Surveyor. Two-dimensional clusters of thermal inertia and albedo reflect the thermophysical attributes of the dominant materials on the surface. In this paper three automated, non-deterministic, algorithmic classification methods are employed for defining thermophysical units: Expectation Maximisation of a Gaussian Mixture Model; Iterative Self-Organizing Data Analysis Technique (ISODATA); and Maximum Likelihood. We analyse the behaviour of the OPEN ACCESS Remote Sens. 2014, 6 5185 thermophysical classes resulting from the three classifiers, operating on the 2007 TES thermal inertia and albedo datasets. Producing a rigorous mapping of thermophysical classes at ~3 km/pixel resolution remains important for constraining the geologic processes that have shaped the Martian surface on a regional scale, and for choosing appropriate landing sites. The results from applying these algorithms are compared to geologic maps, surface data from lander missions, features derived from imaging, and previous classifications of thermophysical units which utilized manual (and potentially more time consuming) classification methods. These comparisons comprise data suitable for validation of our classifications. Our work shows that a combination of the algorithms-ISODATA and Maximum Likelihood-optimises the sensitivity to the underlying dataspace, and that new information on Martian surface materials can be obtained by using these methods. We demonstrate that the algorithms used here can be applied to define a finer partitioning of albedo and thermal inertia for a more detailed mapping of surface materials, grain sizes and thermal behaviour of the Martian surface and shallow subsurface, at the ~3 km scale.