Background: Polyaromatic hydrocarbons (PAHs) are a class of toxic compounds commonly found in edible vegetable oils as a result of contamination through food processing. Among the wide variety of PAHs existing in edible oils, benzo(a)pyrene (BAP), benzo(a)anthracene (BAA), benzo(b)fluoranthene (BBF) and chrysene (CHR) are commonly monitored due to their toxicity, carcinogenic and teratogenic properties. Materials and Methods: In this context, we described a combination of liquid-liquid extraction and dual cartridge solid-phase extraction (dSPE) system for the extraction of BAP, BAA, BBF, and CHR in palm oil derived tocotrienol rich fraction (T3RF), followed by their analysis using GC-MS operating in selected ion monitoring mode (SIM). Results: The separation was effected using a DB-5HT column (30 m × 0.250 mm × 0.25 µm) that can operate at a high temperature limit of 400 °C, which enables the separation of the PAHs in < 28 min. The calibration curves were correlated within the range of 1.5–25 µg/ L, with detection limits (S/N: 3) of 0.48–1.35 µg/L, and relative standard deviations of ≤ 0.07% and ≤ 6.85% were achieved for intra-day retention times and peak areas. Conclusion: The proposed sample preparation and GC-SIM workflow greatly reduces interference caused by tocotrienol homologues and enables the quantitative determination of BAP, BAA, BBF, and CHR in T3RF and palm fatty acid distillates.