This study aimed to assess the characteristics of particulate matter (PM) and polycyclic aromatic hydrocarbons (PAHs) from various stationary and mobile emission sources in Taiwan, with a focus on source apportionment and associated health risks. The northern power plant, equipped with bag filters operating at 150 °C, had significantly lower FPM and CPM levels (0.44 and 0.13 mg/m3, respectively) compared to the central and southern power plants, which used electrostatic precipitators operating at 250 °C (FPM, 1.45–8.35 mg/m3; CPM, 2.37–3.73 mg/m3). Additionally, emissions from diesel vehicles under both idle and high-speed conditions exhibited higher FPM levels (3.46–4.67 mg/m3) than gasoline vehicles (0.19–0.40 mg/m3). In terms of PAH toxicity, diesel vehicle emissions had significantly higher BaP-TEQ (87.3 ng/m3) and BaP-MEQ (25.9 ng/m3) levels compared to power plants (BaP-TEQ, 5.49 ng/m3; BaP-MEQ, 2.65 ng/m3). The highest ambient concentrations of PM2.5, BaP-TEQ, and BaP-MEQ were recorded at traffic sites, with values of 48 ± 36 µg/m3, 0.29 ng/m3, and 0.11 ng/m3, respectively. Differences in PAH distributions between stationary and mobile sources were influenced by factors such as pollution control technologies, combustion temperatures, and fuel types. Diesel vehicle emissions were dominated by benzo[g,h,i]perylene (BghiP), indeno[1,2,3-cd]pyrene (IND), benzo[a]pyrene (BaP), and benzo[b]fluoranthene (BbF) under idle conditions, while phenanthrene (PA), pyrene (Pyr), and BghiP were prevalent under high-speed conditions. Source apportionment conducted using principal component analysis (PCA) and positive matrix factorization (PMF) identified diesel and gasoline vehicles as the dominant contributors to atmospheric PAHs in Taiwan, accounting for 38% of the total, followed by coal-fired power plants at 35%. The highest lifetime excess cancer risk (ECR) of 2.5 × 10⁻5 was observed in traffic-dense areas, emphasizing the public health implications of vehicle emissions. The study adds credibility to the source apportionment findings, and the health risk analysis highlights variations across different regions, including traffic, urban, rural, and background zones.