The invention provides a coffee slag valuable component separation and recovery method and application, and relates to the field of comprehensive utilization of coffee slag. The coffee slag valuable component separation and recovery method comprises pyrolyzing the dried coffee slag at least twice, to be more specific, pyrolyzing the coffee slag under the condition of 190-210DEG C, separating and recovering a first pyrolysis product preferably including caffeine; continuing heating up, pyrolyzing the firstly-pyrolyzed coffee slag under the condition of 290 to 410 DEG C for pyrolysis for at least one time, and respectively separating and recovering pyrolysis products; continuing heating up, and using water vapor to activate the pyrolyzed pyrolysis slag. The method is easy to operate, highly-controllable, reusable in resources, and environmentally-friendly, can be used for mass production. According to the application of the coffee slag valuable component separation and recovery method, the caffeine and pyrolysis oil can be recovered, and the application range of the coffee slag can be broadened.