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(Mg, Fe)SiO₃orthopyroxene is an abundant mineral of oceanic subducting slabs. In‐situ high‐pressure and high‐temperature single‐crystal X‐ray diffraction has been used to investigate the phase transition of orthopyroxene across the enstatite‐ferrosilite (En‐Fs) join (En₇₀Fs₃₀, En₅₅Fs₄₅, En₄₄Fs₅₆and Fs₁₀₀) up to 24.3 GPa and 800 K, simulating conditions within the coldest part of a subduction zone consisting of an old and rapidly subducting slab. Instead of the orthopyroxene → high‐pressure clinopyroxene transition, the α‐opx → β‐opx and β‐opx → γ‐opx phase transition are observed at 7.2–15.3 and 11.6–21.1 GPa (depending on the Fs content), respectively. This study indicates that the pressure‐induced phase transition of (Mg, Fe)SiO₃orthopyroxene under relatively low temperature (<800 K) could be different than those occurring under relatively high temperature (>800 K). Additionally, the α‐opx → β‐opx → γ‐opx phase transition could exist within the center of the extremely cold slabs (like Tonga), where such low temperature persists to ~600‐km depth.