The growth of secondary organic aerosols (SOA) is a vital cause of the outbreaks of winter haze in North China. Intermediate volatile organic compounds (IVOCs) are important precursors of SOA. Therefore, the chemical characteristics, source, and SOA production of IVOCs during haze episodes have attracted much attention. Hourly time resolution IVOC samples during two haze episodes collected in Hebei Province in North China were analyzed in this study. Results showed that: (1) the concentration of IVOCs measured was within the range of 11.3~85.1 μg·cm−3 during haze episodes, with normal alkanes (n-alkanes), polycyclic aromatic hydrocarbons (PAHs), branched alkanes (b-alkanes), and the residue unresolved complex mixture (R-UCM) accounting for 8.6 ± 2.3%, 6.8 ± 2.2%, 24.1 ± 3.8%, and 60.5 ± 6.5% of IVOCs, respectively. NC12-nC15 in n-alkanes, naphthalene and its alkyl substitutes in PAHs, b-alkanes in B12–B16 bins, and R-UCM in B12–B16 bins are the main components, accounting for 87.0 ± 0.2%, 87.6 ± 2.9%, 85.9 ± 5.4%, 74.0 ± 8.3%, respectively. (2) Based on the component characteristics of IVOCs and the ratios of n-alkanes/b-alkanes in emission sources and the hourly variation of IVOCs during haze episodes, coal combustion (CC), biomass burning (BB), gasoline vehicles (GV), and diesel vehicles (DV)were identified as important emission sources of IVOCs in Hebei Province. (3) During haze episodes, temporal variation of the estimated SOA production based on different methods (such as IVOCs concentration, OC/ECmin tracer, and the PMF model) were similar; however, the absolute values were different. This difference may be due to the transformation of IVOCs to SOA affected by various factors such as SOA production from different IVOC components, meteorological conditions, atmospheric oxidation, etc.