Infrared attenuated total reflection (ATR) spectroscopy is a common laboratory technique for the analysis of highly absorbing liquids or solid samples. However, ATR spectroscopy is rarely found in industrial processes, where inline measurement, continuous operation, and minimal maintenance are important issues. Most materials for mid-infrared (MIR) spectroscopy and specifically for ATR elements do not have either high enough infrared transmission or sufficient mechanical and chemical stability to be exposed to process fluids, abrasive components, and aggressive cleaning agents. Sapphire is the usual choice for infrared wavelengths below 5 µm, and beyond that, only diamond is an established material. The use of diamond coatings on other ATR materials such as silicon will increase the stability of the sensor and will enable the use of larger ATR elements with increased sensitivity at lower cost for wavelengths above 5 µm. Theoretical and experimental investigations of the dependence of ATR absorbances on the incidence angle and thickness of nanocrystalline diamond (NCD) coatings on silicon were performed. By optimizing the coating thickness, a substantial amplification of the ATR absorbance can be achieved compared to an uncoated silicon element. Using a compact FTIR instrument, ATR spectra of water, acetonitrile, and propylene carbonate were measured with planar ATR elements made of coated and uncoated silicon. Compared to sapphire, the long wavelength extreme of the spectral range is extended to approximately 8 μm. With effectively nine ATR reflections, the sensitivity is expected to exceed the performance of typical diamond tip probes.