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Phase transition at the initial solidification stage notably affects subsequent phase structure of peritectic alloys, however, detailed dynamics between entangled three-phase region remains ambiguous in the far-from-equilibrium condition during laser additive manufacturing. Here, in-situ peritectic phase transition during single-layer laser printing of an exemplary 304L stainless steel is directly investigated and quantified at high temporospatial resolution by high-speed synchrotron X-ray diffraction and imaging. These quantitative observations clarify the mechanism of coupled peritectic growth and local remelting at three-phase region. The results revealed provide in-depth understanding of phase transformation dynamics and delicate design of phase structure for metal additive manufacturing.