Ferroelectric copolymer thin film PVDF-TrFE was deposited by spin coating method, and then annealed for the improved crystallization. The XRD and AFM measurements showed that as-formed PVDF-TrFE thin film was composed of the nanocrystallines with 50-80 nm in size and some amorphous phases. Meanwhile, as-formed PVDF-TrFE thin films also show a good polarization inversion property with a switch current of approximately 2.0 microA at a coercive field 40 MV/m. Electron emission testing results showed that under a continuous excitation of applied voltage pulses, PVDF-TrFE thin films exhibited an expected electron emission ability with emission current range of 0.08-0.52 microA, and the related electron emission mechanism was discussed.