Bioaccessible fractions of particle-bound hydrophobic organic compounds (HOCs) are critical to evaluating human inhalation exposure risk. However, the key factors for controlling the release of HOCs into the lung fluid are not adequately examined. To address this issue, eight particle size fractions (0.056–18 μm) from different particle emission sources (barbecue and smoking) were collected and incubated with an in vitro method for determining inhalation bioaccessibilities of polycyclic aromatic hydrocarbons (PAHs). The bioaccessible fractions of particle-bound PAHs were 35–65% for smoke-type charcoal, 24–62% for smokeless-type charcoal, and 44–96% for cigarette. The size distributions of bioaccessible fractions of 3–4 ring PAHs were symmetric with the patterns of their masses, characterized as a unimodal distribution with both the trough and peak at 0.56–1.0 μm. Analysis from machine learning showed that chemical hydrophobicity appeared to be the most significant factor affecting inhalation bioaccessibility of PAHs, followed by organic carbon and elemental carbon contents. Particle size seemed to have little effect on the bioaccessibility of PAHs. A compositional analysis of human inhalation exposure risk from total concentration, deposition concentration, and bioaccessible deposition concentration in alveolar region showed a shift in the key particle size from 0.56−1.0 μm to 1.0–1.8 μm and an increasing in the contributions of 2–3 ring PAHs to risk for cigarette due to the high bioaccessible fractions. These results suggested the significance of particle deposition efficiency and bioaccessible fractions of HOCs in risk assessment.