In this study, methodologies for the rational organization of air pollution monitoring network were examined by understanding the characteristics of temporal and spatial distribution of secondary air pollution, whose significance would increase hereafter. The data on $O_3$ and $NO_2$ concentrations during high ozone period in 1998~1999 recorded at the nine air pollution monitoring station in Busan were analysed using principal component analysis (PCA) and cumulative semivariogram. It was found that the ozone concentration was deeply associated with the daily emission characteristics or the $O_3$ precusors, and nitrogen dioxide concentration largely depends on the emission strength of regional sources. According to the spatial distribution analysis of ozone and nitrogen dioxide in Busan using cumulative semivariograms, the number of monitoring stations for the secondary air pollution can be reduced in east-west direction, but reinforced in north-south direction to explain the spacial variability. More scientific and rational relocation of air pollution monitoring network in Busan would be needed to investigate pollution status accurately and to plan and implement the pollution reduction policies effectively.