This paper discusses the problem of thermocycling effect of light-curing polymer–ceramic composites. Cyclic thermal shocks were simulated in laboratory conditions. As a rule, these loads were supposed to reproduce the actual conditions of biomaterials exploitation. Periodically variable stresses occurring in dental restorations are associated with the wear of cold and hot foods and beverages. They lead to changes in the properties of composites, including the properties of the surface layer. The aim of the work was to assess the impact of cyclic hydrothermal interactions on the properties of the surface layer of composites relevant to the operational quality. Two commercial materials manufactured by the world’s leading producer (3M ESPE)—Filtek Z550, Filtek Flow and two experimental, micro-hybrid and flow type composites marked Ex-mhyb(P) and Ex-flow(P), respectively. All tests were carried out before and after hydro-thermal cycles (flowing water thermocycling). Micro-hardness test using the Vickers method, indentation hardness, and resistance to tribological wear in a ball–disc system in sliding friction conditions were performed. In addition, observations of the surface layer of composites on the SEM (scanning electron microscope) were carried out. It was noticed that semi-liquid composites, containing a smaller amount of filler, retain higher stability of mechanical and tribological properties of the surface layer under cyclic hydro-thermal loads. Coefficient of friction of samples after hydro-thermal cycles increased for micro-hybrid materials and Filtek Flow (FFlow) composite. In the case of Ex-flow(P) material, the coefficient of friction decreased. The microhardness of composites also changed, the variability of this size depended on the type of material. Composites with a higher content of filler particles were characterized by greater variability of microhardness under the influence of thermocycles. The resistance to tribological wear also changed in a similar way. Composites containing higher volume fraction of inorganic filler showed higher tribological wear after thermocycling. The wear resistance of flow composites changed to a lesser extent, after thermocycling increased. The paper also showed that, in real kinematic nodes, the surface layer of light-curing ceramic–polymer composites is exposed to significant non-tribological (erosive, thermal, and chemical) defects that synergize with tribological ones. In slip pairs loaded dynamically, under mixed friction conditions, tribological wear of PMCCs (polymer matrix ceramic composites) is manifested by spalling (spalling of the material flakes, in particular the polymer phase) and pitting (crushing wear caused by wear products, in particular large filler particles or clusters, previously adhesively extracted).