The purpose of this study was to optimize V content of TiSiN/TaVN nanomultilayers. TiSiN/TaVN nanomultilayers with various V contents were deposited on 304 stainless steels and Si wafers. The structures and properties of TiSiN/TaVN nanomultilayers were analyzed and characterized. The results show that TiSiN/TaVN nanomultilayers exhibit the face-centered cubic (FCC) structure and preferred orientation on the (111) and (200) planes. With the increasing of V contents, the diffraction peaks of TiSiN/TaVN nanomultilayers were shifted to larger angles. Paralleling to the growth direction of TiSiN/TaVN nanomultilayers, an alternating stress fields are generated to enhance their strength. The hardness and elastic modulus of the nanomultilayers firstly increases and then decreases and friction coefficient firstly decreases and then increases with increasing of V contents. TiSiN/TaVN nanomultilayer with 15 at.% V content indicates the maximum hardness of 27.23GPa, the maximum elastic modulus of 280.96GPa and the highest resistance against plastic deformation. TiSiN/TaVN nanomultilayer with 15 at.% V content has minimum friction coefficient of 0.16 because Magnéli phase oxide V2O5 is formed during the reciprocating sliding friction process and H3/E2 of TiSiN/TaVN nanomultilayer with 15at.% V content is highest.