With the rapid economic growth of China, environmental pollution has become one of the most widely concerned issues. The air pollution in economy fast developing area has appeared regional and complex behavior by the accumulation and coupling of multi pollutants from various sources. Although many ambient air quality monitoring stations are established in urban area, the ground surface pollutant levels are limited to give the whole picture of the air pollution and reveal its real evolution process, chemical reaction scheme and regional transportation. It brings some confusion to the public by the mismatch of air quality index with the sense of atmospheric visibility. Several advanced optical and spectroscopic techniques and an integrated spatio-temporal air quality monitoring system based on these techniques are introduced, which are applied to monitor the particulate matter regional transport flux, gaseous pollutant emission flux from area sources and distribution of vertical columns of trace gases in a large area. The partly measurement results obtained during the 2008 Beijing Olympic Games are presented. The monitoring method and techniques applied for the regional and complex air pollution study are also discussed.