NiTi/Nb layered heterogeneous structure (LHS) materials with different layer spacings were designed and fabricated using composite wire arc additive manufacturing. The NiTi/Nb LHS samples consisted of NiTi phase and β-Nb phase, and no other intermetallic compounds were formed. The NiTi layer in the NiTi/Nb LHS sample changes from a homogeneous eutectic microstructure to a gradient heterogeneous eutectic microstructure as the layer thickness increases. The Nb layer grains are much smaller than the NiTi layer grains, and no obvious texture is formed in the NiTi/Nb LHS samples. NiTi/Nb LHS samples still have a certain recoverable strain at room temperature, with a maximum recoverable strain of 4.36 % after 10 cycles of 10 % strain compression. The wear rate of the NiTi layer of the NiTi/Nb LHS samples was lower than that of the Nb layer. The main wear mechanisms on the Nb surface are abrasive wear, adhesive and oxidative wear while the main wear mechanism on the NiTi surface is adhesive wear. When the layer thickness ratio of NiTi layer to Nb layer is 2:1, the NiTi/Nb LHS samples form a gradient heterogeneous eutectic structure in the NiTi region, which in turn enhances the wear resistance of the LHS samples. In this study, cross-scale NiTi alloy and Nb heterogeneous components were constructed by wire arc additive manufacturing, which showed good wear resistance. The design provides a new solution for integrated additive manufacturing repair of heterogeneous metals in engineering applications.