This paper proposes an accurate physical layer technique to uniquely identify the links of a power line communication network. First, the power line communications (PLC) multipath channel characterization is presented and detailed. Then, a multipath channel delay detection technique is introduced to provide an accurate physical layer identification (PL ID) for the considered PLC links. The accuracy and efficiency are tested by evaluating the successful path detection probability (SPDP) in a simulated scenario under both perfect and imperfect channel state information conditions. The results confirm the advantages of the proposed scheme. Indeed, for a common PLC noise power around 90 dBuV, the provided accuracy reaches ≈90%, while for a noise power below 80 dBuV, the accuracy plateaus at 100%. Overall, the low complexity of the proposed approach and its staggering performance results pave the way for further possible applications in both the PLC and the security domain.