Solid oxide fuel cells (SOFCs) are highly efficient energy conversion devices. However, the sulfur poison, which deteriorates traditional Ni-based anodes, restricts commercialization of the technology. Here, layered perovskite oxide NaYTiO₄ was prepared using solid-state method and modified by partial substitution with different valence ions. Properties of NaYTiO₄ before and after doping were systematically studied. Ni was doped into the perovskite layer and contributed to forming NaYTi_0.95Ni_0.05O₄, which regulated growth characteristics of the crystal and in-situ exsoluted in reduction conditions. Two-dimensional distribution of alkali metals and polar structures in the material provides advantages, including excellent chemical water absorption capacity and good sulfur-resistance. With an increased chemisorbed oxygen species of 64.5%, Ni-doped material becomes more outstanding. SOFC with NaYTi_0.95Ni_0.05O₄ as composite anode showed superior electrocatalytic activity. The peak power density reached 183.8 mW·cm^-2 at 800 ℃ with H₂ as fuel. Furthermore, the power density increased by 25.2% with an addition of 0.1% H₂S in H₂. The modified cell could work stably even at 700 ℃, a more toxic condition, for 40 h without significant poisoning effect. These results indicate that the modified layered perovskite oxides are excellent sulfur-resistance anodes.