Graphite was functionalized electrochemically in a potassium fluoride solution and used to prepare polyimide (PI)/graphene nanohybrid films. The as-made electrochemically fluorinated graphene (EFG) was used to prepare nanohybrid films with colorless PI, which was synthesized from 4,4 ′ -(hexafluoroisopropylidene) diphthalic anhydride and bis(trifluoromethyl) benzidine by in situ polymerization. The surface functionalization of graphite was characterized by powder XRD, TEM with energy dispersive X-ray spectroscopy elemental mapping, X-ray photoelectron spectroscopy, Raman spectroscopy, and TGA. The microstructure of the films was characterized by Fourier transform IR spectroscopy, XRD and SEM. The film properties were measured using a universal testing machine, TGA, dynamic mechanical analysis, four-point probe, UV-visible spectroscopy and water contact angle analysis. EFG improved the tensile strength and modulus of the nanohybrid films by 20% and 50%, respectively. The glass transition temperature and electrical conductivity of the nanohybrid films were 12 ∘ C and nine orders of magnitude higher than those of the neat PI film, respectively. The nanohybrid film maintained 80% optical transmittance even after the addition of 0.1 wt% EFG.