A simple, rapid, and reliable headspace solid-phase microextraction (HS-SPME) procedure, reinforced by applying vacuum in the extraction vial, was developed. It was applied for the extraction of nicotine in solid samples prior to determination by gas chromatography-flame ionization detection (GC-FID). First, the surface of a narrow stainless steel wire was made porous and adhesive by platinization to obtain a durable, higher surface area, and resistant fiber. Then, a thin film of sulfonated graphene/polyaniline (Sulf-G/PANI) nanocomposite was synthesized and simultaneously coated on the platinized fiber using the electrophoretic deposition (EPD) method. It was demonstrated that the extraction efficiency remarkably increased by applying the reduced-pressure condition in the extraction vial. To evaluate the conventional HS-SPME and vacuum-assisted HS-SPME (VA-HS-SPME) platforms, all experimental parameters affecting the extraction efficiency including desorption time and temperature, extraction time and temperature and moisture content of sample matrix were optimized. The highest extraction efficiency was obtained at 60 °C, 10 min (extraction temperature and time) and 280 °C, 2 min (desorption condition), for VA-HS-SPME strategy, while for conventional HS-SPME the extraction and desorption conditions found to be 100 °C, 30 min and 280 °C, 2 min, respectively. The Sulf-G/PANI coated fiber showed high thermal stability, good chemical/mechanical resistance, and long lifetime. For analysis of nicotine in solid samples using VA-HS-SPME-GC-FID, linear dynamic range (LDR) was 0.01–30 μg g−1 (R2 = 0.996), the relative standard deviation (RSD%, n = 6), for analyses of 1 μg g−1 nicotine was calculated 3.4% and limit of detection (LOD) found to be 0.002 μg g−1. The VA-HS-SPME-GC-FID strategy was successfully carried out for quantitation of nicotine in hair and tobacco real samples.