Relay synchronization is a collective state, originally found in chains of interacting oscillators, in which uncoupled dynamical units synchronize through the action of mismatched inner nodes that relay the information but do not synchronize with them. It is demonstrated herein that relay synchronization is not limited to such simple motifs, rather it can emerge in larger and arbitrary network topologies. In particular, we show how this phenomenon can be observed in networks of chaotic systems in the presence of some mismatched units, the relay nodes, and how it is actually responsible for an enhancement of synchronization in the network.