Fine road dust is a major source of potentially toxic elements (PTEs) pollution in urban environments, which adversely affects the atmospheric environment and public health. Two different sizes (10–63 and <10 μm) were separated from road dust collected from Apia City, Samoa, and 10 PTEs were analyzed using inductively coupled plasma mass spectrometry (ICP-MS). Fine road dust (<10 μm) had 1.2–2.3 times higher levels of copper (Cu), zinc (Zn), arsenic (As), cadmium (Cd), antimony (Sb), lead (Pb), and mercury (Hg) than 10–63 μm particles. The enrichment factor (EF) value of Sb was the highest among PTEs, and reflected significant contamination. Cu, Zn, and Pb in road dust were also present at moderate to significant levels. Chromium (Cr), cobalt (Co), and nickel (Ni) in road dust were mainly of natural origins, while Cu, Zn, Sb, and Pb were due to traffic activity. The levels of PTEs in road dust in Samoa are lower than in highly urbanized cities, and the exposure of residents in Samoa to PTEs in road dust does not pose a noncarcinogenic health risk. Further studies of the effects of PTEs contamination in road dust on the atmosphere and living organisms are needed.