This research intends to explore the short-term impacts of PM_2.5/O₃ on daily death in Hefei from 2013 to 2018. Data on daily death of Hefei residents, meteorological factors, and air pollutants were collected from Jan 1, 2013, to Dec 31, 2018. The correlation between PM_2.5/O₃ and daily death in Hefei during the research period was studied by time series analysis. From 2013 to 2018, there were 61,683 non-accidental deaths, including 27,431 cardiovascular deaths, 5587 respiratory deaths, 20,921 malignant tumor deaths, and 1674 diabetes deaths, in Hefei. Annual mean concentrations of PM_2.5, PM₁₀, NO₂, SO₂, CO, and O₃ in Hefei were 66.18, 92.37, 39.75, 15.39, 930, and 79.08 μg m⁻³, respectively. An increase of 10 μg m⁻³ in PM_2.5 was related with 0.53% (95% CI 0.31–0.75%), 0.93% (95% CI 0.60–1.26%), 0.90% and (95% CI 0.23–1.57%) increase in non-accidental, cardiovascular and respiratory diseases mortality, respectively. The association between ozone and mortality was not significant. In cold seasons, PM_2.5 had a stronger effect on the deaths resulting from non-accidental, cardiovascular, and respiratory diseases. The effect of O₃ on deaths was not significantly different between the cold season and the warm season. Women and the elders (over 65 years) were at high risk of being affected by PM_2.5/O₃. Short-term exposure to PM_2.5 was positively correlated with increased deaths due to non-accidental, cardiovascular and respiratory diseases in Hefei. Females and elders were more vulnerable to PM_2.5/O₃ exposure. No significant associations were observed between ozone and deaths from non-accidental, cardiovascular, respiratory, malignant tumors, and diabetes diseases.