(AlCrTiZrMox)N coatings with varying Mo content were successfully prepared using a multi-target co-deposition magnetron sputtering system. The results reveal that the Mo content significantly affects the microstructure, hardness, fracture toughness, and tribological behavior of the coatings. As the Mo content in the coatings increases gradually, the preferred orientation changes from (200) to (111). The coatings consistently exhibit a distinct columnar structure. Additionally, the hardness of the coatings increases from 24.39 to 30.24 GPa, along with an increase in fracture toughness. The friction coefficient is reduced from 0.72 to 0.26, and the wear rate is reduced by 10 times. During the friction process, the inter-column regions of the coatings are initially damaged, causing the wear track to exhibit a wavy pattern. Greater frictional heat is generated at the crest of the wave, resulting in the formation of a MoO2 lubricating layer. The friction reaction helps to reduce the shear force during friction, demonstrating the lower friction coefficient of the (AlCrTiZrMox)N coatings. Both the hardness and fracture toughness work together to reduce the wear rate, and the (AlCrTiZrMox)N coatings show excellent wear resistance. Most notably, although the columnar structure plays a negative role in the hardness, it contributes greatly to the wear resistance.