This study examines the levels of benzene and the potential health impact during three years of continuous monitoring (2019–2021), including the COVID-lockdown period from 2020 in a city that is an important Romanian center for petroleum refining and associated product manufacturing. The dataset contains benzene, toluene, NOx, PM10 concentrations, and meteorological factors monitored by six automatic stations from the national network of which four are in the city and two outside. Special attention was given to the benzene dynamics to establish patterns related to the health impact and leukemia. An assessment of the exposure was performed using EPA’s ExpoFIRST v. 2.0 for computing the inhalation Average Daily Dose (ADD) and Lifetime Average Daily Dose (LADD). The health impact was estimated based on several indicators such as lifetime cancer risk (LCR), Hazard Quotient (HQ), Disability-Adjusted Life Years (DALY), and Environmental burden of disease (EBD). Overall, the annual average of all stations was almost similar between years i.e., 3.46 in 2019, 3.41 in 2020, and 3.63 µg/m3 in 2021, respectively. The average of all stations during the lockdown period was 2.67 µg/m3, which was lower than the multiannual average of the 2019–2021 period, i.e., 3.5 µg/m3. Significant correlations were present between benzene and other pollutants such as NOx (r = 0.57), PM10 fraction (r = 0.70), and toluene (r = 0.69), and benzene and temperature (r = −0.46), humidity (r = 0.28), and wind speed (r = −0.34). Regarding the ADD, in all scenarios, the most affected age categories are small children, despite a lower outdoor exposure time. From birth to <70 years, the ADD varied depending on the exposure scenario resulting in 3.27 × 10−4, 5.6 × 10−4, and 4.04 × 104 mg/kg-day, and 3.95 × 10−4, 10.6 × 10−4, and 6.76 × 10−4 mg/kg-day for the LADD, respectively. The Integrated Lifetime Cancer Risk (ILTCR) values were 14.1 × 10−5 in winter, 9.04 × 10−5 in spring, 8.74 × 10−5 in summer, and 10.6 × 10−4 in autumn. The ILTCR annual averages were 1.08 × 10−4 (2019), 1.07 × 10−4 (2020), 1.04 × 10−4 (2021), and 1.06 × 10−4 for the entire period. The resulting ILTCR values point out very risky conditions, with the annual averages reaching the definite cancer risk category. The corresponding burden based on the DALY’s loss due to leukemia in Ploieşti was estimated at 0.291 (2 μg/m3 benzene), 0.509 (3.5 μg/m3 benzene), 0.582 (4 μg/m3 benzene), and 0.873 DALYs per 100,000 inhabitants (6 μg/m3 benzene), respectively. The current study provides useful insights for a better understanding of the exposure levels to benzene and associated health impact in Ploieşti despite the limitations determined by the data hiatus and incomplete or missing information regarding the health impact.