Quantum internet gives the promise of getting all quantum resources connected, and it will enable applications far beyond a localized scenario. A prototype is a network of quantum memories that are entangled and well separated. In this Letter, we report the establishment of postselected entanglement between two atomic quantum memories physically separated by 12.5 km directly. We create atom-photon entanglement in one node and send the photon to a second node for storage via electromagnetically induced transparency. We harness low-loss transmission through a field-deployed fiber of 20.5 km by making use of frequency down-conversion and up-conversion. The final memory-memory entanglement is verified to have a fidelity of 90% via retrieving to photons. Our experiment makes a significant step forward toward the realization of a practical metropolitan-scale quantum network.