Chemical compositions of atmospheric fine particles like PM2.5 prove harmful to human health, particularly to cardiopulmonary functions. Multifaceted health effects of PM2.5 have raised broader, stronger concerns in recent years, calling for comprehensive environmental health-risk assessments to offer new insights into air-pollution control. However, there have been few studies adopting local air-quality-monitoring datasets or local coefficients related to PM2.5 health-risk assessment. This study aims to assess health effects caused by PM2.5 concentrations and metal toxicity using epidemiological and toxicological methods based on long-term (2007–2017) hourly monitoring datasets of PM2.5 concentrations in four cities of Taiwan. The results indicated that (1) PM2.5 concentrations and hazardous substances varied substantially from region to region, (2) PM2.5 concentrations significantly decreased after 2013, which benefited mainly from two actions against air pollution, i.e., implementing air-pollution-control strategies and raising air-quality standards for certain emission sources, and (3) under the condition of low PM2.5 concentrations, high health risks occurred in eastern Taiwan on account of toxic substances adsorbed on PM2.5 surface. It appears that under the condition of low PM2.5 concentrations, the results of epidemiological and toxicological health-risk assessments may not agree with each other. This raises a warning that air-pollution control needs to consider toxic substances adsorbed in PM2.5 and region-oriented control strategies are desirable. We hope that our findings and the proposed transferable methodology can call on domestic and foreign authorities to review current air-pollution-control policies with an outlook on the toxicity of PM2.5.