Commonly used endoprostheses in the orthopedic industry are those made of Ti6Al4V titanium alloy. Unfortunately, this material has low abrasion resistance, and therefore methods of their modification are still sought. A sensible approach is coating the alloy with a layer of a polymer having higher abrasion resistance. The adhesion of polymers to alloy is low, therefore the alloy requires prior modification. In this work, the alloy was modified with three types of diazonium salt and the influence of substituent on the effectiveness of modification was determined. Then, five or ten polyurethane layers were attached to the surface of the modified alloy. Using Raman mapping, the uniform distribution of layers was proved. Layers are stable in simulated human body fluids. The effectiveness of attaching subsequent layers of polyurethane was also confirmed by nanoindentation. The main focus of this work was to improve the wear resistance of the titanium alloy. The obtained results indicate that the titanium alloy with a polyurethane layer has almost ten times lower coefficient of friction compared to pure alloy. Such a low value has not been described in the literature so far. These results are the first step for obtaining endoprostheses with very high abrasion resistance.