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Similar to Si3N4 ceramics, β→α phase transformation in SiC ceramics plays a key role in tailoring the microstructures thus optimizing related properties. SiC microstructures are dominated with the core–rim structures by AlN-solution, and by EBSD analysis, α-lamellae were revealed as stacking-faults (SF) and twin-boundaries (TB) in β-grains, co-existing with the core–rim structures as α/β→α’/β’ transformation by sintering. The structural transformation can proceed much further by gas-pressure-sintering than hot-pressing with only RE2O3 agents, while the latter retain a high-density of SF/TB in the metastable β-SiC grains. By high-angle secondary-electron imaging, nanoscale transition-layer (TL) was observed as an inter-phase to fully separate the core and rim, which is created by a transitory equilibrium in the solution–reprecipitation process. The enrichment of AlN or RE in TL demonstrates their segregation to core surface until reaching the super-saturation and before the growth of rims. With higher AlN or RE solution and after sintering, a shear stress can develop from TL contour to drive the expansion of SF/TB in Martensitic transition, especially under an external isotropic pressure. The combinations of β→α transformation, core–rim structures and viscous liquid-phase enable the comprehensive assessment of sintering–microstructure–property–performance relationship of SiC ceramics, as demonstrated for their creep behaviors and fracture toughness.