Given the lack of research on the schoolchildren exposure to PM2.5-bound PHAs in northeast China, we investigated the effects of exposure to ambient benzo[b]fluoranthene (BbFA) and dibenz[a,h]anthracene (DahA) bound to PM2.5 on pulmonary ventilation dysfunction (PVD) and small airway dysfunction (SAD). PM2.5 samples at two schools (A and B) were collected, and the concentrations of PM2.5-bound 4–6-ring PAHs were analyzed. PVD and SAD were evaluated by pulmonary function tests in 306 students while urinary MDA and CRP levels were measured. The results confirmed that ambient PM2.5-bound 4–6-ring PHA levels were significantly higher and the PVD and SAD incidence in schools A and B were increased during the heating season. We found that PM2.5-bound BbFA, BkFA, BaP, and DahA levels were only correlated with SAD in schoolchildren; the correlation coefficients of BbFA and DahA were the highest effect estimates, possibly due to altered MDA levels. Therefore, this research enables us to better understand the effects of exposure to ambient PM2.5-bound PHAs on pulmonary function parameters. Our results also showed that identification of hazardous PM2.5-bound BbFA and DahA to health is crucial for preventing the respiratory-related diseases.