We have been developing new analytical techniques using resistive type thermal probes, as employed in scanning thermal microscopy (SThM), to implement different measurement mechanisms. The same active sensor is used to probe chemical, morphological and physical properties of the surface of materials with high spatial resolution. As well as providing passive (temperature) and active (thermal properties) mapping of the surface of a sample, the probe is used to perform localised thermo‐mechanical measurement similar to that achieved by bulk techniques such as differential scanning calorimetry (DSC) and thermo‐mechanical analysis (TMA). Photothermal infrared micro‐spectroscopy and spatially resolved pyrolysis mass spectrometry are also implemented by interfacing a scanning probe microscope to a FTIR spectrometer and a mass spectrometer respectively. An approach to multiple analysis, based on proximal probe methodology and using the same sensor to obtain different information from precisely the same area is thus established. Effective data correlation and identifications of species is hence possible with high spatial resolution. The techniques, their implementation and continuous development are described and typical results obtained from measurements on polymeric materials are presented. © 2003 American Institute of Physics