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To study the precipitation mechanism of α-Cr phase in Inconel 718 alloy, the samples after long-time aging at 650 and 677℃ were examined by microstructural observations and chemical phase analysis methods. Combining the thermodynamics and kinetics calcula-tion results, α-Cr always precipitates in the vicinity of δ phase, because δ phase rejects Cr into theγ-matrix when growing. The selected area diffraction patterns confirm that the crystallographic relationships of α-Cr with δ phase are (010) δ//(-110)α -Cr and [100] δ//[111] δ-Cr. A graphic model is also presented to show the crystallographic relation between α-Cr and δ phases.