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A rational utilization of land is a matter of importance in sustainable development of mountainous area. The land function in mountainous areas has a close connection with space structure of ecology, production and living. To promote a harmonious development of the relationship between people and nature in mountainous areas, it is necessary to coordinate their relationships of space functions. Suitability evaluation of basic unit function associated with multi-scale space analysis is a prerequisite to a reasonable optimization of land function structure. In this study, an optimized evaluation index system of combination functions was introduced into the assessment of ecological spatial functional suitability in ecological fragile regions by adding three indicators, namely, soil erosion sensitivity, landscape ecological risk and ecological sensitivity. The principle of “taking high” (referred to a function with high suitability to be regarded as the main function of an evaluation unit) and ecological priority (referred to the case, supposing the suitability of a unit’s three functions is consistent, the main function is determined to be the ecological function) were used to determine the main function of an evaluation unit. Pingshan County, China, located at the eastern foot of the Taihang Mountain, was targeted in this case study. The production-living-ecology space (PLES) function in Pingshan was identified by applying our improved valuation indexes. Further, the functional suitability distribution of the combination of elements was obtained by using overlapping comprehensive analysis method, considering the tradeoff of the functional suitability of combination elements. The regions suitable for production/living were distributed in relatively flat piedmont plains, whereas the regions suitable for ecology were distributed in the mountain areas of middle and low altitudes. Therefore, to maintain a sustainable development in mountainous areas, an improved scheme of development for Pingshan should be to delineate ecologically fragile areas, to build ecological industrial parks near existing scenic spots, to protect basic agricultural production areas, and to increase investment in science and technology, including reasonable ecological compensation. This study can provide reference for the planning of sustainable development in the Taihang Mountain area and similar regions.