Polyacrylonitrile (PAN) nanofibers were prepared by electrospinning and coated with zeolitic imidazolate framework-8 (ZIF-8) by a phase conversion growth method and investigated for CO₂ capture. The PAN nanofibers were pre-treated with NaOH, and further coated with zinc hydroxide, which was subsequently converted into ZIF-8 by the addition of 2-methyl imidazolate. In the resulting flexible ZIF-8/PAN composite nanofibers, ZIF-8 loadings of up to 57 wt% were achieved. Scanning electron microscopy and energy-dispersive X-ray spectroscopy (EDS) showed the formation of evenly distributed submicron-sized ZIF-8 crystals on the surface of the PAN nanofibers with sizes between 20 and 75 nm. X-ray photoelectron spectroscopy (XPS) and carbon-13 nuclear magnetic resonance (¹³C NMR) investigations indicated electrostatic interactions and hydrogen bonds between the ZIF-8 structure and the PAN nanofiber. The ZIF-8/composite nanofibers showed a high BET surface area of 887 m² g⁻¹. CO₂ adsorption isotherms of the ZIF-8/PAN composites revealed gravimetric CO₂ uptake capacities of 130 mg g⁻¹ (at 298 K and 40 bar) of the ZIF-8/PAN nanofiber and stable cyclic adsorption performance.