We present flexible transparent and highly conductive ultra-thin silver films using an amine-containing nonconjugated polyelectrolytes (NPEs) as a nuclei inducer. In general, thermally evaporated silver on dielectric substrates forms granular-like non-continuous films below the percolation threshold thickness (~15 nm) because of the surface energy mismatch between the two materials. By applying amine-containing NPEs as a nucleation inducer, the coordination bonds between silver and amines in the NPE lead to the formation of well-ordered metal nuclei, resulting in continuous ultra-thin silver films. Optical and electrical performances of electrodes are significantly improved with increasing contents of amine in nuclei inducers because coordination bonds between silver and amines are well formed in the amine-rich film. By using NPEs as a nuclei inducer and a conductive polymer as a facile antireflection layer, we obtain high quality flexible and transparent electrodes that exhibit high transmittance of 92% at 550 nm and a superior sheet resistance of 9 Ω/□. The polymer light emitting diodes using NPE/silver/conducting polymer electrode achieve comparable performance to devices employing indium tin oxide.