Most of present works are centering on synthesizing covalent organic framework (COF) with different shapes and modifying surfaces to improve lubricating property in oils, while little attention is paid to design special monomers and realize multifunction beyond lubrication. Herein, a multifunctional COF lubricating system that possesses long-time dispersing stability without any surface modification and achieves NIR responsiveness and effective lubrication, is unprecedentedly developed. To build the system, special donor and acceptor (D-A) structured monomers are employed to enhance NIR absorption, conversion and facilitate charge movement and transport. The porous structure and enriched alkyl chain guarantees robust dispersing stability of COF in various oils, and high specific surface area stores and releases oils during friction process. The ball-like structure, high mechanical strength and formation of solid-liquid complex lubrication state make COF applicable to various working conditions for more than 10800 cycles. 0.36 wt% addition of COF reduces friction coefficient and wear rate by 11% and 79.8%, and polishing/repair effect as well as formation of protective lubrication film contribute to the long-time lubrication performance. Our work establishes a new strategy to construct D-A structured COF with excellent photothermal responsiveness and dispersibility without any further surface modification, and demonstrate its first application in reducing friction and wear in oil.

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