In this study, polyimide (PI)-based carbon nanofibers (CNFs) were prepared via electrospining polyamic acid solutions followed by thermal imidization and carbonization. And its versatile adsorption performance for removal of 2,4-dichlorophenol (2,4-DCP), methylene blue (MB) and tetracycline (TC) was evaluated. PI-based CNFs with a high specific surface area of 715.89m2g−1 exhibited a maximum adsorption of 483.09mgg−1, 272.48mgg−1 and 146.63mgg−1 for 2,4-DCP, MB and TC, respectively. The MB adsorption efficiency was highly pH-dependent with an optimal pH 11, while the CNFs performed well towards TC and 2,4-DCP adsorption in the wide pH range of 4–7 and 3–7. Kinetics and isotherm experiments were fitted well with pseudo-second-order kinetics model and Langmuir model, respectively. Thermodynamic parameters showed that adsorption was spontaneous and endothermic. Moreover, the reusability of PI-based CNFs was evaluated, and the result showed that the removal of 2,4-DCP, TC and MB was kept its high efficiency after 5 consecutive cycles. This study demonstrated that the CNFs should be a powerful adsorbent for the removal of a great number of organic pollutants from aqueous environments.