Spin-glass theory serves as a quintessential framework for studying complex systems in statistical physics. Central to this theory is replica symmetry breaking, a distinctive phase transition between paramagnetic and spin-glass states, which has emerged as a pivotal concept for identifying nontrivial correlated states. To date, optical analogies of replica symmetry breaking have predominantly relied on intensity fluctuations, largely overlooking polarization as the inherent mapping of photonic spin. Here we propose an effective statistical method by mapping the optical polarization states onto a continuous classical spin model. We experimentally identify the emergence of a polarization replica symmetry breaking during the buildup of mode locking. Our findings, supported by numerical simulations, suggest that polarization replica symmetry breaking dynamics may represent a broader feature of ultrafast photonic systems and offer a route to studying their statistical mechanical behavior. The discovery offers profound insights into photonic polarization replica symmetry breaking states and the intricate polarization dynamics governing mode-locking processes.

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• Chaos
• Nonlinear optics
• Optical transient phenomena
• Optics & lasers