Although PAN has ong been considered to belong to one of the most characteristic photooxidants, its concentra-tions have rarely been measured in a systematic manner in Korea. The first in-situ Measurements of PAN were made in concert with simultaneous analysis of NO, NO$_2$, $O_3$ and UV-Visible radiation intensity from Seoul and dong-Hae during Spring and early Summer of 1999. The aim of our study was to evaluate the behavior of photo-chemical species in a highly polluted urban air and a relative clean one. PAN were determined using a semi-auto-mated gas chromatograph equipped with an electron captured detection system. Calibration of the PAN was done by synthesizing liquid standards using a strong acid nitration of the corresponding peracid. The PAN concentra-tions were found in the range of a few ppbv in the urban air ad persistently less than a ppbv in the clean rural airs. Diurnal variations of PAN and $O_3$ were also observed consistently during the experiment with maxima occurring during the late daylight hours. While the positive dependency of $O_3$ production and PAN concentrations were ob-served in most occasion, the dependency became deviated significantly under changes in air masses.