This paper uses concept and method of ecosystem servicing values to establish an estimating system of water-energy-food servicing values, which is used to estimate its servicing values of Guizhou's water-energy-food on economy and ecology and their ties. The gross servicing values is stable with declining. The servicing value of water resource lies in moderation of natural ecology and plays a critical role on the gross servicing values. Energy has a larger positive servicing value on social economy, but at a much larger negative ecological cost, which is the root cause of falling servicing value of WEF. The servicing values of food is increasing, providing a support to supply of social economy. The servicing value of WEF tie in Guizhou is small and unstable, so it suggests Guizhou fulfill water resources advantages in order to stabilize its servicing values. Boosting the servicing value of energy to social economy needs to prevent its impact on natural ecology, and to prevent panel pollution on food production, and to develop tourism and ecological agriculture. Moreover, moderation of WEF tie to improve the stability of system.