Matter‐light interaction is at the center of diverse research fields from quantum optics to condensed matter physics, opening new fields like laser physics. A magnetic exciton is one such rare example found in magnetic insulators. However, it is relatively rare to observe that external variables control matter‐light interaction. Here, we report that the broken inversion symmetry of multiferroicity can act as an external knob enabling the magnetic exciton in van der Waals antiferromagnet NiI₂. We further discover that this magnetic exciton arises from a transition between Zhang‐Rice‐triplet and Zhang‐Rice‐singlet's fundamentally quantum entangled states. This quantum entanglement produces an ultra‐sharp optical exciton peak at 1.384 eV with a 5 meV linewidth. Our work demonstrates that NiI₂ is two‐dimensional magnetically ordered with an intrinsically quantum entangled ground state.

https://onlinelibrary.wiley.com/doi/10.1002/adma.202109144