In recent years, acid rain has been a social problem all over the world. In Japan, it is also a big problem especially in the metropolitan area. Then, we have measured major ions such as H+, Na+, NH4+, K+, Mg2+, Ca2+, Cl−, NO3−, and SO42− in precipitation and dry deposition samples which had been collected at 9 sampling sites at Hiyoshi, Mita, Kashiwa, Shiki, Fujisawa, Yokosuka, Mitaka, Hachiouji, and Ashikaga in Tokyo Metropolitan area for 10 years since 1990. The average pH of precipitation in their sites was 4.56 (n=1906). As the results of multiple regression analysis showed that pH of precipitation was determined by 5 ions such as NH4+, nssCa2+(non sea salt calcium), nssCl−(non sea salt chloride), NO3−, nssSO42−(non sea salt sulfate) in the most of the sampling sites. Therefore, it is very important to investigate the behavior of these ions to understand the acidification of rain in Tokyo Metropolitan area. In this study, a long term trend of each ion concentration in precipitation and wet deposition was also investigated the base on the data we had observed at 7 sites for 10 years by the statistical method.