Intermediate-volatility organic compounds (IVOCs) serve as pivotal precursors to secondary organic aerosol (SOA). They are highly susceptible to substantial wall losses both in indoor environments and within smog chambers even with Teflon walls. Accurately characterizing the wall loss effects of IVOCs is thus essential for simulation studies aiming to replicate their atmospheric behaviors in smog chambers to ensure precise modeling of their physical and chemical processes, including SOA formation, yet a comprehensive understanding of the wall loss behavior of IVOCs remains elusive. In this study, we conducted a thorough characterization of wall losses for typical intermediate-volatility hydrocarbon compounds, including eight normal alkanes (n-alkanes) and eight polycyclic aromatic hydrocarbons (PAHs), using the smog chamber with a 30 m3 Teflon reactor. Changes in the concentrations of gaseous IVOCs with the chamber were observed under dark conditions, and the experimental data were fitted to the reversible gas–wall mass transfer theory to determine the key parameters such as the wall accommodation coefficient (αw) and the equivalent organic aerosol concentration (Cw) for different species. Our results reveal that Cw values for these hydrocarbon IVOCs range from 0.02 to 5.41 mg/m3, which increase with volatility for the PAHs but are relative stable for alkanes with an average of 3.82 ± 0.92 mg/m3. αw span from 1.24 × 10−7 to 1.01 × 10−6, with the values for n-alkanes initially showing an increase followed by a decrease as carbon numbers rise and volatility decreases. The average αw for n-alkanes and PAHs are 3.34 × 10−7 and 6.53 × 10−7, respectively. Our study shows that IVOCs exhibit different loss rates onto clean chamber walls under dry and dark conditions, with increasing rate as the volatility decreases. This study demonstrates how parameters can be acquired to address wall losses when conducting smog chamber simulation on atmospheric processes of IVOCs.