Ordered surface step arrays were successfully prepared on two different types of miscut yttria-stabilized zirconia (YSZ) substrates via one-step pre-annealing. These steps were subsequently used as templates for the self-assembly of the nanoislands, which results in significantly improved alignment of the islands along the step direction. Additionally, a unique step faceting phenomenon at island growth front was observed only on the (001)–[100] miscut YSZ substrates. Preliminary investigation indicates that this faceting is induced by doping via surface diffusion, while the elastic interaction between the faceted steps also plays an important role.