A novel method of investigating the temperature dependent variation of aspects of the complex refractive index n* in samples in the THz range using continuous, non-polarised, synchrotron radiation is presented. The method relies on the use of ATR apparatus, and retains the advantage of minimal sample preparation, which is a feature of ATR techniques. The method demonstrates the viability of rapidly monitoring temperature reflectance whilst continuously heating or cooling samples by using a temperature variable Thermal Sample Stage. The method remains useful when the refractive index of the sample precludes attenuated total reflection study. This is demonstrated with the water reflectance experiments. The temperature dependent ATR reflectance of tissue-representative fats (lard and Lurpak® butter) was investigated with the novel approach. Both are within the ATR range of the diamond crystal in a “true” ATR mode. Lard showed no clear temperature variation between -15 0C and 24 0C at 0.7 to 1.15 THz or 1.70 to 2.25 THz. Lard can be regarded as having invariable, constant, dielectric properties within mixtures when biological substances are being assessed for temperature dependent dielectric variation within the stated THz ranges. Lurpak® butter (water content 14.7%) displayed temperature dependent reflectance features with a steady decline in reflectivity with increasing temperature. This is in line with the temperature-dependent behaviour of liquid water. There is no rapid change in reflectance, even at -20 0C, suggesting that emulsified water retains liquid-water-like THz properties at freezing temperatures.