Flexible materials with balanced dielectric as well as conductive characteristics have elucidated considerable demand in field of research where conventional dielectric or insulators can be replaced by recent advances in various electronics appliances. Our work describes the detailed analyses of dielectric properties like dielectric constant, losses, and electric modulus by means of broadband dielectric spectroscopy over frequency ranging from 0.1 Hz to 10 MHz and temperature ranging from 0 to 60 °C for poly(vinyl alcohol)‐polyaniline (PVA‐PANI) free standing electrospinning nonwoven mat. It has been contemplated that the dielectric constant was enhanced by increasing PANI concentration for complete range of frequency at room temperature. The enhanced dielectric constant value (5.14 at 0.1 Hz, 2.66 at 1 KHz, 2.58 at 10 KHz, and 2.19 at 10 MHz) was anticipated for 7 wt % loading of PANI which was attributed to the presence of dipoles and interfacial polarization enclosed by the polymers. The increased dielectric constant with PANI dosing as well as with temperature attributed to favorable interfacial polarization. Shifting of peak is noticed in the spectra of imaginary electric modulus with increase in temperature which indicates increased chain dynamics of polymers in the mat. Three‐dimensional analysis of the field emission scanning electron microscopy images was carried out by SPIP analytical software. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 135, 46121.