Capabilities of the Attenuated Total Reflection (ATR) at THz wavelengths for increased sub-surface depth characterisation of (bio-)materials is presented. The penetration depth of a THz evanescent wave in biological samples is dependent on the wavelength and temperature and can reach 0.1-0.5 mm depth due to strong refractive index change ∼0.4 of the ice-water transition; this is quite significant and important when studying biological samples. Technical challenges are discussed when using ATR for uneven, heterogeneous, high refractive index samples with possibility of frustrated total internal reflection (a breakdown of the ATR reflection-mode into transmission-mode). Local field enhancements at the interface are discussed with numerical/analytical examples. Maxwell’s scaling was used to model behaviour of absorber-scatterer inside materials at the interface with ATR prism for realistic complex refractive indices of bio-materials. Modality of ATR with polarisation analysis is proposed and its principle illustrated, opening an invitation for its experimental validation. The sensitivity of the polarised ATR mode to the refractive index between the sample and ATR prism is revealed. Design principles of polarisation active optical elements and spectral filters are outlined. The results and concepts are based on experiments carried out at the THz beamline of the Australian Synchrotron.