Multiqubit entanglement is an indispensable resource for quantum information science. In particular, the entanglement of photons is of conceptual interest due to its implications in measurement-based quantum computing [1-3], communication [4][5][6][7], and metrology [8,9]. The traditional way of spontaneous parametric downconversion already demonstrates entanglement of up to a dozen photons [10] but is hindered by its probabilistic nature. Here, we experimentally demonstrate an efficient approach for multiphoton generation with a Rydberg superatom, a mesoscopic atomic ensemble under Rydberg blockade [11]. Using it as an efficient singlephoton interface [12], we iterate the photon creation process that gives rise to a train of temporal photonic modes entangled in photon number degree [13]. We detect the multiphoton entanglement via converting the photon number degree to a time-bin degree. Photon correlations verify entanglement up to 12 modes. The efficiency scaling factor for adding one photon is 0.27, surpassing previous results [10,[14][15][16], and can be increased significantly without fundamental limitations.