Polycyclic aromatic hydrocarbons (PAHs) are a class of ubiquitous and persistent organic compounds that are significantly teratogenic, carcinogenic and mutagenic. Rubber stoppers commonly used in sterile formulation packaging materials often contain carbon black as the additive to enhance mechanical strength. However, PAHs may be formed during the production of carbon black, which could cause the drug formulations to be contaminated when contacting with the rubber stopper, and then enter the patient's body. The determination of PAHs in drug formulations is challenging, due to their trace amounts and matrix interference. Therefore, sample pretreatment is necessary and important. In this work, a novel technique, named in-vial solid-phase extraction (IVSPE), was developed for the selective extraction and enrichment of 16 PAHs in pharmaceuticals. The coated sample vial was directly used as the container for the whole process of sample pretreatment. As the solid-phase adsorbent, the coating was prepared by successively modifying the inner surface of a sample vial with polydopamine film and octadecylamine. PAHs could be selectively extracted through π-π stacking interaction and hydrophobic interaction, and then desorbed and enriched by a small amount of organic solvent. After systematic optimization of the coating preparation and the extraction process, the limits of detection and quantification of 16 PAHs were in the range of 0.002-0.60 ng mL-1 and 0.007-2.00 ng mL-1, respectively. Good linearities and precision of six repeated injections were obtained. The recoveries at three spiked concentration levels in normal saline were in the range of 62.72-106.90% with the relative standard deviation between 0.83% and 6.78%. Finally, PAHs in normal saline and powders for injection were extracted by established IVSPE, followed by separation and detection with high-performance liquid chromatography with a fluorescence detector and diode array detector (HPLC-FLD/DAD). It is worth noting that the preparation conditions of the adsorbent in the IVSPE method are mild, simple and green. Moreover, IVSPE has the advantages of having few work steps and avoiding the risk of contamination, because no special instrumentation or sample transfer is required. IVSPE could also be used for the pretreatment of multiple samples at the same time, which is beneficial to practical applications.