In this paper the comparative studies on structural, mechanical and corrosion properties of Nb2O5/Ti–Al–V and graphene/Ti–Al–V alloy systems have been investigated. We show that the hardness of pure niobium pentoxide was ca. 8.64GPa and graphene deposited on titanium alloy surface was equal 5.63GPa. However, the graphene monolayer has no effect on surface hardness of titanium alloy and can be easily removed from the surface. On the other hand, the sample with graphene coating has much better corrosion resistance. Our results suggest, that the use of combined layers of niobium pentoxide and graphene, in the hybrid multilayer system can greatly improve the mechanical and corrosion properties of the titanium alloy surface. Such hybrid system can be used in the future, as protection coating for Ti alloy, in biomedical application and in other applications, where Ti alloys work in an aggressive corrosive environment and in engineering applications where friction is involved. •Corrosion properties of Nb2O5/TiAlV and graphene/TiAlV systems were investigated.•Nb2O5 thin film improves titanium alloy surface hardness from 5.64GPa to 8.64GPa.•Nb2O5 thin film improves corrosion resistance of Ti6Al4V in aggressive environment.•icorr for graphene monolayer deposited on Ti6Al4V surface decreases to 0.01μA/cm2.•Graphene monolayer caused decrease in the electrochemical activity of the Ti surface.