The dielectric behavior of polyacrylonitrile derived carbon nanofibers formed at different carbonization temperatures was investigated using impedance spectroscopy. The impedance data are presented in the form of Cole-Cole plots and four equivalent electrical circuits are derived. It is found that by increasing carbonization temperature from 500 to 800 degrees C, a strong capacitive element in the parallel equivalent circuit is transformed into an inductive element, while the contact resistance and parallel resistance are significantly decreased. Along with the morphological and chemical structural evolution, respectively witnessed by scanning electron microscopy and Raman spectroscopy, the dielectric transition deduced from the transformation of electrical circuits can be correlated to the proposed microstructural changes of polyacrylonitrile derived carbon nanofibers and the interaction/interference among them.