X-ray photoelectron spectroscopy (XPS) technique was utilized to study the correlation between the tendency of Sn surface segregation and the crystallographic orientation of grain surface in coarse-grained (0.2–0.8 mm in diameter) Zircaloy-4 specimen. The results indicated that the intensity of Sn surface segregation was in an order of sn=01694332&md5=c6119043f29b527f1626663cccb97cf6">, and it was in agreement with the prediction from bond-breaking theory.