Fine particulate matters (PM_(2.5)) has been identified as one of the major air pollutants in urban areas, which are responsible for the adverse effects on public health and the deterioration of visibility. New PM_(2.5) air quality standards were promulgated in Taiwan on 14^(th) May 2012, as well as the standard sampling and analytical method for atmospheric PM_(2.5) (NIEA A205.11C) on 24^(th) April 2012. In this study, the atmospheric levels and characteristics of PM_(2.5) in Tainan during 2013 were evaluated by measuring the mass concentration of PM_(2.5) and analyzing the water-soluble ionic, carbon, and metal components. Additionally, a Chemical Mass Balance (CMB) receptor model was used to identify possible sources of PM_(2.5) and their contributions. Based on results of this study, the current PM_(2.5) levels in Tainan in spring and winter (41–49 μg m^(–3)) were substantially higher than the yearly average PM_(2.5) air quality standards (15 μg m^(–3)). According to chemical composition analysis, secondary aerosols (NH_4^+, NO_3^-, and SO_4^(2–)) contributed approximately 50% and 60% of PM_(2.5) mass in spring and winter respectively; but were responsible about 40% by mass in summer at both Tainan and Xinying stations. From the results of CMB model, the main contribution sources to the PM_(2.5) in Tainan are traffic emissions (31.5%), ammonium sulfate (25.5%), ammonium nitrate (12.5%), and crustal elements (11%). Consequently, to improve PM_(2.5) of Tainan City, the priority control pollutants (or sources) are primary PM_(2.5) (open burning, construction sites and road dust by vehicles), NO_x (diesel vehicle emissions), and SO_x (fuels).