Since air quality monitoring data sets are important base for developing of air quality management strategies including policy making and policy performance assessment, the environmental protection authorities need to organize and operate monitoring network properly. Air quality monitoring network of Busan, consisting of 18 stations, was allocated under unscientific and irrational principles. Thus the current state of air quality monitoring networks was reassessed the effect and appropriateness of monitoring objectives such as population protection and sources surveillance. In the process of the reassessment, a GIS-based decision support system was constructed and used to simulate air quality over complex terrain and to conduct optimization analysis for air quality monitoring network with multi-objective. The maximization of protection capability for population appears to be the most effective and principal objective among various objectives. The relocation of current monitoring stations through optimization analysis of multi-objective appears to be better than the network building for maximization of population protection capability. The decision support system developed in this study on the basis of GIS-based database appear to be useful for the environmental protection authorities to plan and manage air quality monitoring network over complex terrain.