<p>To effectively mitigate the inherent trade-off between wear resistance and toughness in DLC coatings, this study explores a novel multilayer design. A soft–hard alternating multilayer DLC coating with tailored periodic parameters was successfully deposited on 5A06 aluminum alloy via direct current pulsed (DCP) magnetron sputtering combined with anode layer ion beam technology, enhancing its adaptability to extreme environments. The tribological properties of the coatings in the range of room to low temperatures were then investigated in depth. The findings indicate that, in comparison with a single-layer structure comprising a soft coating, the structural design of an alternating soft and hard multilayer DLC coating exhibits considerable advantages in tribological performance at ambient to low temperatures. By optimizing layer thickness and parameter control, the multilayer structure effectively enhances the overall performance of the coating, exhibiting superior tribological properties in comparison with a single-layer DLC coating. Of particular note is the tribological performance of sample S5, which exhibits excellent wear resistance and stability of the coefficient of friction within the room temperature to low-temperature range. Moreover, the wear mechanism of DLC coatings at low temperatures is the result of the interaction of several factors, primarily involving the formation of the transfer film, the stability of the coating structure, the embrittlement of the material due to low temperatures, the icing effect, and the inhibition of chemical reactions. This research establishes a robust foundation for DLC coatings’ utilization in challenging operational environments.</p>