In this paper, it was found that with the addition of sodium dodecyl sulfate (SDS, a hydrophilic surfactant) and oleic acid (OA, a lipophilic surfactant) in a solvent with a proper composition ratio, a stable gel could be obtained via a simple ultrasonic treatment. The synergistic gelation of OA–SDS was verified in a series of solvents with different polarities, such as white oil (WO), LB-2000, n-hexane, polyalphaolefin (PAO10), and deionized water. The Fourier transform infrared (FTIR) analysis confirms that the gelation of OA–SDS is highly related to the ion exchange reaction between them. However, the xerogel of OA–SDS gelator in deionized water and WO (OSW) exhibited remarkably different morphologies, indicating that the gelation is based on different molecular assembly processes, which is governed by the orientation of the two surfactant molecules in liquid media. Further characterizations of OSW gel presented that the synergistic effect between OA and SDS not only existed in gelation, but also in enhancing the mechanical and thermal stability of WO, and endowing the OSW gel with reliable friction reduction and antiwear performances under variable working conditions. Subsequently, the lubrication mechanism was proposed based on rheological analysis and the morphological and compositional analysis of wear surfaces. This study provides a novel idea for the molecular design of lubricating gelators with wide adaptability to solvent polarity and working conditions.