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In this work, the concept of optical identification (OI) based on physical unclonable functions is introduced for the first time, to our knowledge, in optical communication systems and networks. The OI assigns an optical fingerprint and the corresponding digital representation to each sub-system of the network and estimates its reliability in different measures. We highlight the large potential applications of OI as a physical layer approach for security, identification, authentication, and monitoring purposes. To identify most of the sub-systems of a network, we propose to use the Rayleigh backscattering pattern, which is an optical physical unclonable function and allows OI to be achieved with a simple procedure and without additional devices. The applications of OI to fiber and path identification in a network and to the authentication of users in a quantum key distribution system are described.