In the present study two organic guest host system are being explored for electronic applications based on 2-methyl 4-nitroaniline (2-mNA)/polymethylmethacrylate (PMMA) and 2-mNA/ polyethersulfone (PES). Freestanding poled polymeric films have wide applications in nonlinear optics and in various photonics applications. Exploring dielectric capability of these films can be beneficial for many opto, electro and photonic applications. Low power loss is an essential characteristic for any electronic element and has been a challenging job for researchers and scientists. Forwarding in this direction, this paper focuses on capacitance of unpoled and poled polymeric films. Dissolving limit of guest material into polymer without showing any segration of guest material has been optimized for both host polymers. Capacitance is measured with different dose of 2-mNA by using 4294A Agilent Impedance Analyzer at room temperature. Here we are only manipulating the results that are optimized at 1K Hz frequency. It is observed that capacitance increases with increasing 2-mNA content into polymer but PMMA/2-mNA system shows more dielectric strength than PES/2-mNA system. The impact of half an hour contact poling by using 6KV/cm DC electric field at 120°C temperature on dielectric capability is also optimized. It is observed that how; to be poled the guest host films can affect the dielectric strength of both polymeric systems. Without describing electric power consumption in terms of power loss, electrical quality of any component is incomplete. Thatswhy dissipation factor have been evaluated for both guest host system at 1K Hz frequency. Dissipation factor rises with the 2-mNA doping concentration but after poled the films, it reduces drastically. PES/2-mNA system showed low power loss than PMMA/2-mNA system. The structural characterizations of all films are carried out by XRD, which shows an amorphous nature of PES/2-mNA and PMMA/2-mNA film samples. Absorbance measured by UV-Vis Spectroscopy reveals that undoped film samples has high transmittance in the UV-Vis region and doped film samples shows absorption band up to 450 nm. The films are characterized by Scanning Electron Microscopy and FT-IR Spectroscopy for bulk properties evaluation.