TiSiN/AlN nanomultilayers with different thicknesses of AlN layer were deposited on 304 stainless steel by magnetron sputtering system. X-ray diffraction, nanoindentation tester, atomic force microscopy, and friction wear tester were used to characterize microstructure and properties of TiSiN/AlN nanomultilayers. The results show that TiSiN/AlN nanomultilayers are face-centered cubic structures and exhibit a strong preferred orientation on (200) plane. The diffraction peaks of TiSIN/AlN nanomultilayer shift to a small angle. When the thickness of the AlN layer is 2 nm, the peak is highest, and the shift degree is biggest. The alternating tension and compression stress fields are formed along the growth direction of TiSiN/AlN nanomultilayers and increase the strength of the namomultilayers. When the thickness of the AlN layer is 2 nm, the maximum hardness and Young’s modulus of TiSiN/AlN nanomultilayers are, respectively, 32.8 GPa and 472 GPa, and the smallest roughness is 33.4 nm. But the friction coefficient is smallest when the thickness of the AlN layer is 1.5 nm.