An environmentally benign approach was developed to fabricate cyclic polyamidine via polymerization in supercritical carbon dioxide (SCCO2) and subsequently amidinization in water. Synthetic parameters were evaluated using response surface methodology. In comparison with aqueous solution polymerization for the fabrication of PNVF-co-PAN, polymerization using SCCO2 is favorable to promote the yield and viscosity of PNVF-co-PAN and diminished reaction time on account of excellent solvation capacity and transport property of SCCO2. Replacing the traditional water solution with SCCO2 as a green solvent could heighten the purity of PNVF-co-PAN by virtue of the excellent extraction of SCCO2. The cationic degree (5.66 mmol/g) of polyamidine fabricated by environmentally benign approach was significantly higher than that in previous reported studies.