First-order phase transitions of black holes have been extensively studied within thermodynamic frameworks, yet the corresponding evolution of spacetime geometric properties remains unclear. This paper establishes a purely differential geometric framework to probe such phase transitions by analyzing the curvature of unstable null orbits. Using the geodesic curvature of the null circular orbit in the optical metric to locate the light ring, we demonstrate that the corresponding Gaussian curvature K serves as a direct geometric signature of the phase transition. During a first-order phase transition, the curve K versus temperature T exhibits a multivalued structure within the spinodal region, precisely mirroring the swallowtail behavior of the free energy. Numerical analysis of Hayward-Letelier-AdS black holes confirms the effectiveness of this geometric signature. Our work demonstrates that the intrinsic geometric quantities of spacetime encode the information of black hole phase transitions. These quantities serve as geometric probes of black hole phase transitions, while their discontinuity between the small and large black hole branches exhibits order parameter-like behavior. As an extension of this geometric probe, we also find that the Gaussian curvature exhibits a heat–capacity–like divergence at the second–order phase transition point. These results provide a purely geometric foundation for understanding the correspondence between thermodynamics and spacetime curvature in the null case.