Environmental barrier coatings (EBCs) consisting of a tri-layer structure (Si/Mulltite/ Yb₂SiO₅) were prepared on SiC/SiC ceramic matrix composite (CMC). For decreasing degradation of water-oxygen corrosion for SiC/SiC CMC, a novel EBCs fabrication method of plasma spray-physical vapor deposition (PS-PVD) was proposed in this work. Prior to EBCs preparation, agglomerated Yb₂SiO₅ powders were fabricated by spray dryer. After that dense EBCs were fabricated by PS-PVD technique, where the Yb₂SiO₅ coating with laminar and columnar composited structure was achieved. And the deposition diagram of this special structure was presented. Besides, the thermal cycle performance of PS-PVD EBCs was tested from 1300℃ to room temperature water. No apparent spallation appeared after 30 cycles, which showed the EBCs had a good thermal shock performance.