This paper proposes a rational approximation-based approach to find positive real parameters for the extended Debye model (EDM), aimed at condition assessment of insulation systems of power transformers. The EDM can model the slow and fast polarization phenomenon, including relaxation mechanisms with different relaxation times within a composite dielectric material. In the proposed approach, the complex permittivity of the transformer’s composite insulation is approximated via rational functions, as given by the vector fitting (VF) software tool, and the EDM parameters are identified from the obtained poles/residues. To guarantee positive real parameters, i.e., a physically realizable circuit, VF is internally modified to calculate the final residues of the rational approximation via a constrained linear least-squares problem without resorting to further post-processing algorithms, as in existing methods, hence without affecting fitting accuracy. The effectiveness of the parametrized EDM is demonstrated in two ways: (a) by reconstructing frequency domain spectroscopy (FDS) curves provided via measurements in new oil-immersed power transformers and (b) by the comparison of the calculated polarization current given by EDM versus real measurements in time domain. The achieved fitting accuracy in most of the cases is above 99 percent for the reconstructed FDS curves, while the polarization current waveform is reproduced with good agreement.