Diamondlike carbon (DLC) films have emerged as a class of very important tribological materials in recent years mainly because of their outstanding properties, such as high mechanical strength and hardness, excellent chemical inertness, and exceptional friction and wear performance under both dry and lubricated sliding conditions. Persistent and systematic research efforts during the last decade have resulted in the development of a new breed of DLC films providing superlubricity and near-wearless sliding even under very harsh contact and environmental conditions. In fact, the dry sliding friction and wear coefficients (i.e., as low as 0.001 and 10-11 mm3/N.m, respectively) of these films are among the lowest reported to date, and such unusual tribological properties may have huge positive impacts on efficiency, durability, and performance characteristics of a wide range of mechanical systems, including magnetic hard disks, sliding and/or rolling contact bearings, gears, mechanical seals, scratch-resistant glasses, invasive and implantable medical devices, microelectromechanical systems (MEMS) and many more. In this chapter, we attempt to provide an up-to-date overview of these novel DLC films that can provide superlubricity and discuss in detail those factors that control their very unique lubrication mechanisms. Specifically, we concentrate on the current state-of-the-art in our understanding of their superlow friction and wear mechanisms, and how these mechanisms may relate to their structural chemistry, mechanical properties, and test and environmental conditions. In particular, various intrinsic (film specific) and extrinsic (or test condition-specific) factors that play major roles in friction and wear of DLC films are discussed in detail and correlated with their friction and wear mechanisms.