Hybrid matter-photon entanglement is the building block for quantum networks. It is very favorable if the entanglement can be prepared with a high probability. In this Letter, we report the deterministic creation of entanglement between an atomic ensemble and a single photon by harnessing the Rydberg blockade. We design a scheme that creates entanglement between a single photon's temporal modes and the Rydberg levels that host a collective excitation, using a process of cyclical retrieving and patching. The hybrid entanglement is tested via retrieving the atomic excitation as a second photon and performing correlation measurements, which suggest an entanglement fidelity of 87.8%. Our source of matter-photon entanglement will enable the entangling of remote quantum memories with much higher efficiency.
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