Yb2SiO5/mullite bi-layered coatings are promising environmental barrier coatings, but its molten salt corrosion mechanism is unclear. In this work, Yb2SiO5/mullite bi-layered coatings are fabricated by combining plasma spraying and dip-coating techniques. Residual stresses in the coatings caused by thermo-mechanical interaction are investigated by a nondestructive Raman spectrum method under high-temperature molten salt corrosion. In the as-deposited coatings, the stress in the mullite layer is compressive and the value near Si3N4 substrate is minimum. During high-temperature corrosion test, the residual stress near mullite-substrate interface changes sharply while the stress near mullite-Yb2SiO5 interface is concentrated without large fluctuation. An interfacial phase, YbAlO3, which is formed because of the inter diffusion of Al in the mullite layer and Yb in the Yb2SiO5 layer, causes the stress concentration. The change of SiO2 component in the mullite layer leads to the sharp change of residual stress near the mullite-substrate interface.