In this thesis, we study networks of entangled quantum optical systems at different degrees of complexity, with a special regard to their application to quantum communication scenarios. In quantum communication, we want to allow two or more distant parties to exploit the properties of quantum systems to communicate in a certain way that would be unattainable with classical technology. The archetype of quantum communication is Quantum Key Distribution (QKD), that allows two agents to share a secret random key to perform secure communications, while preventing a third malicious agent from gaining knowledge about their key. In this manuscript, however, we will explore quantum communication scenarios that go beyond standard QKD in order to test the many possibilities offered by interconnected networks of quantum devices, also known as quantum internet. Specifically, we present three different types of quantum networks, that correspond to three levels of complexity of the quantum internet. In each of these levels, we describe the communication scenario, the physical requirements necessary to build the specific architecture and a novel quantum protocol that cannot be reproduced without quantum resources. In this work, we paid particular attention to the “practicality” of the protocols, namely the fact that it should be possible to implement them in realistic conditions with current technology, at least as a proof of principle. The first concerns an interactive proof quantum protocol showing experimental evidence of computational quantum advantage in the interactive setting for the first time. In this scenario, we have a computationally unbounded quantum prover who wants to convince an honest verifier of the existence of a certain solution to a complex mathematical problem, by sending part of the proof in the form of quantum states. Our quantum scheme lets the verifier verify the prover’s assertion without actually receiving the whole solution. We prove that if the agents were not allowed to use quantum resources, the verification protocol would require an exponential time in the size of the solution, leading to a quantum advantage in computational time that we could demonstrate in our laboratory. The second copes with an electronic-voting protocol that exploits an untrusted multipartite entangled quantum source to carry on an election without relying on election authorities, whose result is publicly verifiable without compromising the robustness of the scheme and that can be readily implemented with state-of-the-art technology for a small number of voters. Unlike previous results, our scheme does not require simultaneous broadcasting and works also in noisy scenarios, where the security is bounded by the fidelity of the quantum state being used. Last, we simulate many modes squeezed states as continuous variables Gaussian quantum networks with complex topologies, characterizing their correlations and estimating the scaling of their cost while the networks grow using a squeezing resource theory. We prove a result that allows us to enhance the entanglement between two nodes in the network by measuring the multiple paths linking them and we employ this effect to devise an entanglement routing protocol, whose performance is particularly effective on large complex networks.