Lubricants that are used in miniaturized moving mechanical components generally serve under severe conditions, such as high temperature, high speed, and high load. Although alkyldiphenylethers (ADEs) are used as base oils for high-temperature greases, their tribological properties remain unclear. This study investigated the influence of the alkyl chains on the tribological properties of ADEs. Longer and more attached alkyl chains decreased the friction coefficient of ADEs under both reciprocating and continuous sliding conditions. Wear was found to be independent of the alkyl chain under reciprocating sliding conditions due to abrasion being caused by debris that was not readily removed. ADEs showed good anti-wear properties when used as either a lubricant or an additive under continuous sliding conditions. Much smoother surfaces in the friction track were observed in comparison to poly-α-olefin. Fourier-Transform infrared spectroscopy analysis suggested that the ether groups were attracted to the worn steel surface, phenyl groups became consequently perpendicular, and the attached alkyl chains repelled other substances and prevented further wear of the surface. Moreover, ADEs showed a high adaptability with traditional additives.