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The Stern–Gerlach (SG) effect provided the first direct experimental evidence of the quantization of electron spin. Although some analog SG effects have been proposed in optical systems, finding a perfect optical analog for the SG effect remains a challenge. Here, a novel optical SG effect is demonstrated in periodically poled electro‐optical crystals. Induced by an applied electric field, the principal axes of crystal rock periodically along the propagation direction of light. When the quasi‐phase‐matching condition is satisfied, the electro‐optical coupling process within the periodically poled crystal can be accurately described by the Schrödinger–Pauli equation for spin‐1/2 particles. The output photons can be deflected toward opposite directions according to their intrinsic spin angular momentum (circular polarizations), since the transversely varying duty cycle of crystal arises an effective magnetic‐field gradient. Moreover, the output photons can be separated according to two arbitrary orthogonal polarization states, allowing us to construct high‐speed electro‐optically tunable polarization beam splitters for arbitrary orthogonal polarization states. Therefore, the optical SG effect provides not only a perfect optical analog for the quantum SG effect but also a useful optical element for optics and quantum physics. [ABSTRACT FROM AUTHOR]