We propose a new methodology, namely "quantum Zeno blockade," for managing light scattering at a few-photon level in general nonlinear-optical media, such as crystals, fibers, silicon microrings, and atomic vapors. Using this tool, antibunched emission of photon pairs can be achieved, leading to potent quantum-optics applications such as deterministic entanglement generation without the need for heralding. In a practical implementation using an on-chip toroidal microcavity immersed in rubidium vapor, we estimate that high-fidelity entangled photons can be produced on-demand at MHz rates or higher, corresponding to an improvement of ≳107 times from the state-of-the-art.