As a key role in the acid-deposition and the generation of secondary particle matter (PM), measurement of the concentration of atmospheric ammonia in urban area has been attracting the scientists’ interests nowadays. After studying the special absorption features of ammonia in short UV wavelength range, detailed concernful issues were put forward in the present paper. The decision of using xenon lamp as the light source was made after the evaluation of measurement of light spectroscopy. Retrieval wavelength band for NH3 was fixed from 204 to 214 nm and optimal method of deducting other interferential gases was also shown. A home-made open-path DOAS (OP-DOAS) system was set up for the measurement of the concentration of atmospheric NH3. The detection limit of such system was calculated with the typical noise level as low as 0.33 μg·m-3 with the optical path 228 m. Through field experiment in Guangzhou city, such a system can be competent for the online and high time-resolution monitoring of the concentration of atmospheric ammonia. With a significant diurnal variation, the atmospheric ammonia changed from 0.83 to 3.11 μg·m-3 with the mean value 1.59 μg·m-3. The representative character of the diurnal variation is that the concentration of NH3 peaks during night while drops to bottom in the daytime. After the error analysis procedure, typical measurement accuracy of such OP-DOAS system was within 10%.