In internal combustion piston engines, the formation of an oil film is completely different from that seen in industrial machines. The molecular adhesion force at the interface between the surface coating of engine parts and the lubricating oil determines the load-carrying capacity and the ability to form a lubricated film. The geometry of the lubricating wedge between the surfaces of the piston rings and the cylinder wall is created by the thickness of the oil film and the height of the ring’s coverage with lubricating oil. This condition is affected by many of the parameters that characterize the engine’s operation and the physical and chemical parameters of the coatings used for the cooperating pairs. For lubricant particles that reach energies that are higher than the potential energy barrier regarding adhesive attraction at the interface, slippage occurs. Therefore, the value of the contact angle of the liquid on the surface of the coating depends on the value of the intermolecular force of attraction. According to the current author, there is a strong relationship between the contact angle and the lubrication effect. The paper shows that the surface potential energy barrier is a function of the contact angle and contact angle hysteresis (CAH). The innovation of the current work consists in examining the contact angle and CAH under the conditions of thin layers of lubricating oil, in cooperation with hydrophilic and hydrophobic coatings. The thickness of the lubricant film was measured under various speed and load conditions, using optical interferometry. The study shows that CAH is a better interfacial parameter for correlation with the effect of hydrodynamic lubrication. This paper presents the mathematical relationships relating to a piston engine, various coatings, and lubricants.