Although arsenic contamination of underground water in southern Taiwan is well known, few studies examine atmospheric arsenic deposition in this area, which might be the major source of such pollution to the soil, water, and even underground water. This research focused on the atmospheric arsenic concentration, dry and wet depositions, and the As distribution around Chiayi County, located in the south of Taiwan. Eight sampling sites are used, both upwind and downwind of an area with heavy industrial and human activities. All samples were collected by a PS-1 high volume sampler at each site, pretreated by a digestion process, and further analyzed with an ICP-MS. The results show that the arsenic deposition flux ranged from 65.0 to 473 μg/m2-month in Chiayi County. This deposition flux has no significant seasonal variation, based on the multiple trend results obtained from pooling the dry and wet deposition data. The average dry deposition flux of As ranged from 34 to 161 μg/m2-month during the sampling year, and had the opposite trend to the wind speed. Additionally, the correlations between atmospheric arsenic concentration and PM levels were significant, supported by the low p-value (< 0.01) at a 99% confidence level. Meanwhile, the highly linear correlation between As and PM concentrations was also evaluated. The amount of precipitation was statistically correlated to the wet deposition flux (11.3–414 μg/m2-month with a p-value = 2 × 10–7 and r-value = 0.9306. Furthermore, the composition of the As mass concentrations in ambient air were dominated by As (V) in both fall (66.4%) and winter (68.9%). According to the GIS spatial analysis of the As concentration in the dry season, from October to March, the As contribution of local emissions were not significant. Consequently, this study indicates that the atmospheric As around Chiayi County might be sourced from the upwind northern area, and mainly deposited through wet scavenging.