Polycyclic aromatic hydrocarbons (PAHs), carcinogenic persistent organic compounds, require ultrasensitive detection for health risk assessment of tobacco products. While traditional cigarette smoke contains FDA-monitored PAHs (e.g., benzo [a]pyrene) at ng/cigarette (cig) levels, heated tobacco aerosols exhibit 1-2 orders of magnitude lower PAH concentrations (<0.1 ng/cig), demanding advanced analytical methods. Current approaches involve laborious pretreatment (multi-step purification, solvent concentration) and suffer from matrix interference and insufficient sensitivity. Existing large-volume injection techniques face limitations in aerosol analysis due to matrix complexity or analyte loss. This study introduces a novel large volume thermal injection-column internal evaporation concentration and gas chromatography-triple quadrupole mass spectrometry (LVI-CIEC-GC-MS/MS) platform. Optimized injection parameters enabled direct introduction of 200 μL aerosol extract into a 300°C inlet, coupled with pre-column dynamic condensation equilibration and solvent venting, eliminating tedious pretreatment while enhancing sensitivity. Using Multiple Reaction Monitoring (MRM) mode, the method achieved excellent linearity (R² >0.996) for 16 PAHs, with LOQs of 0.003-0.023 ng/cig (1-2 orders lower than conventional methods), spiked recoveries of 84.6-113.2%, and relative standard deviations (RSDs) <2.8%. Applied to commercial heated tobacco products, PAH levels were quantified at 0.0154-10.035 ng/cig, demonstrating robustness against complex matrices. By integrating large-volume injection, in-column enrichment, and high-selectivity MS/MS, this method overcomes critical challenges in ultra-trace PAH analysis, offering a streamlined, and high-sensitivity platform for evaluating tobacco product risks.