This study introduces a green, cheap, easy to prepare and powerful solid phase microextraction (SPME) sorbent for analytical monitoring applications. Here, graphitic carbon nitride (g-C₃N₄) nanosheets have been prepared on graphenized pencil lead (GPL) as a sorbent by a one-step electrochemical reduction for the first time. GPL not only serves as a fiber platform for g-C₃N₄ but also significantly enhances the immobilization of g-C₃N₄ by π–π interaction, and it enhances the adsorption ability of g-C₃N₄ (∼2 times). Moreover, due to the study of adsorption capacity of g-C₃N₄, PAHs as model analytes were chosen. After the SPME procedure, the extraction phase was injected to HPLC-UV for the determination of PAHs. The prepared fiber with the g-C₃N₄ green sorbent showed ultrasensitive and rapid detection of PAHs with an unprecedented method. The limits of detection (LODs) were in the 0.001–0.1 μg L⁻¹ range in a wide linear range from 0.0025 to 200 μg L⁻¹, while the precision was very satisfactory (maximum relative standard deviation: RSD = 7.8%) considering the non-automated nature of the method. In addition, the real sample analysis showed acceptable recoveries in the range of 78–108%.