The development of very high data-rate power-line communication (PLC) systems requires an accurate knowledge of the transmission phenomena over the electrical network. In particular, the detection of the multiple propagation paths enables a compact description of the channel models, and gives an indication of the network topology, which may, in turn, be exploited to improve the communication techniques over PLC. In this paper, two high-resolution algorithms for the identification of the propagation paths are studied and adapted to the PLC channel characteristics, namely, the frequency-domain maximum-likelihood (FDML) algorithm and the Matrix Pencil (MP) algorithm. A parametric study is then detailed in order to analyze the performance of both algorithms in terms of resolution, computation time, and residual error. The study demonstrates that the MP algorithm provides a quicker convergence and a lower residual error when compared to the FDML algorithm. Finally, the MP algorithm is validated through its application on experimental network measurements. Results show a good agreement between the measurement and the synthetic channel recomposed from the detected paths.