Curvature effects are typically present in the process of additive manufacturing (AM), particularly for wire arc additive manufacturing. In this paper, stainless-steel wire was adopted to deposit thin-walled samples with different curvatures. Optical microscopy, SEM, EDS and micro-hardness was used to analyse the microstructure, composition and properties of the samples. The result shows that the bottom region of the thin-walled sample had a mainly planar and cellular crystal microstructure. For the middle region, the microstructure revealed mainly dendrites, and the top layer has equiaxed dendrite morphology. The microhardness value of the bottom was greater than that of the middle, and the microhardness value of the middle was greater than that of the top. Moreover, the grain size of the inner part (direct to curvature radius) was larger than that of the outer part, and the micro-hardness value exhibited an increasing tendency from the inner to the outer side. With enlarging curvature, the degree of grain size differences and micro-hardness variants decreased. Finally, an investigation with a low carbon steel wire showed that it had a similar curvature effect for its AM specimen.