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Entanglement, the non-local correlations present in multipartite quantum systems, is a key resource for quantum technologies. It is therefore a major priority to develop simple and energy-efficient methods for generating high-fidelity entangled states. In the case of light, entanglement can be realized by interactions with matter but the required nonlinear interaction is often impractically weak. Here we show how a single two-level emitter deterministically coupled to light in a nanophotonic waveguide can be used to realize photonic quantum entanglement by excitation at the single-photon level. Efficient optical coupling enables mediation of two-photon interactions by the emitter, creating a strong nonlinearity that leads to entanglement. We experimentally verify energy–time entanglement by violating a Bell inequality in an interferometric measurement of the two-photon scattering response. The on-chip two-level emitter acts as a passive scatterer, so that no advanced spin control is required. As such, our method may provide a more efficient approach to synthesizing photonic entangled states for quantum simulators or metrology.