Thin-wall samples of 17-4PH stainless steel were prepared by pulsed TIG wire arc additive manufacturing technology (P-TIG WAAM), and the microstructure and mechanical properties of the samples in different regions (bottom, middle, top) were studied. The results show that the microstructure of the thin-wall samples are mainly consisted of martensite matrix embedded by worm-like (bottom) and strip-shaped (top) δ-ferrite, with a small amount of austenite. The δ-ferrite content gradually decreases along the building direction, resulting in a gradual increase in microhardness from the bottom to the top. Along the building direction, the precipitation density and size distribution of nano-scale CRPs (Cu-rich precipitates) in δ-ferrite and martensite, as well as at the δ-ferrite / martensite interface are significantly different: the CRPs in δ-ferrite is precipitated with lower density, larger size, and inhomogeneous distribution at the bottom region, while that in martensite is precipitated with higher density, smaller size, and homogeneous distribution. At the bottom region, a chain of large size fcc-CRPs (∼65 nm) is precipitated along the δ-ferrite / martensite interface to coordinate the strain between them and improve the strength and ductility simultaneously, thus excellent mechanical properties (tensile strength = 1356±24 MPa, elongation =15.16±2.6%) are obtained. The relationship between the evolution of CRPs and the intrinsic heat treatment (IHT) during P-TIG WAAM is also discussed.