Energy dissipation due to friction and wear is reducing the energy efficiency and reliability of mechanical systems. Thus, great efforts are being made to minimize friction for technical applications. In our present work, we investigate the tribological behavior of stainless steel 100Cr6 with a-C:H and a-C:H:Si coating lubricated with a surface-active formanisotropic 1,3-diketone. The results show that superlow friction can be achieved on the tnacroscale using a steel 100Cr6 self pairing (COF similar to 0.005) and with 100Cr6 in combination with a-C:H coating (COF similar to 0.008). Furthermore, the replacement of steel with a-C:H coating leads to a considerable decrease of wear. The reduced COF arises from the chemical interaction of the lubricant with the surface and nascent iron ions. It was found that interfacial parameters correlate with tribological results. In addition, the alignment of the formanisotropic molecules in the tribological contact at thin-film lubrication leads to an anisotropic viscosity with a minimum shear resistance in sliding direction. Atomistic simulation of tribochemical interactions was conducted to derive a friction model based on the thin-film lubrication theory. This investigation indicates the potential to substantially reduce friction and wear using this fluid in real technical applications.