We discover a first-order phase transition in the canonical ensemble of random unlabeled networks with a prescribed average number of links. The transition is caused by the nonconcavity of microcanonical entropy. Above the critical point coinciding with the graph symmetry phase transition, the canonical and microcanonical ensembles are equivalent and have a well-behaved thermodynamic limit. Below the critical point, the ensemble equivalence is broken, and the canonical ensemble is a mixture of phases: empty networks and networks with average degrees diverging logarithmically with the network size. As a consequence, networks with bounded average degrees do not survive in the thermodynamic limit, decaying into the empty phase. The celebrated percolation transition in labeled networks is thus absent in unlabeled networks. In view of these differences between labeled and unlabeled ensembles, the question of which one should be used as a null model of different real-world networks cannot be ignored.