Y2SiO5 has potential applications as a high-temperature structural ceramic and environmental/thermal barrier coating. In this work, we synthesized single-phase Y2SiO5 powders utilizing a solid–liquid reaction method with LiYO2 as an additive. The reaction path of the Y2O3/SiO2/LiYO2 mixture with variation in temperatures and the role of the LiYO2 additive on preparation process were investigated in detail. The powders obtained by this method have good sinterability. Through a pressureless sintering process, almost fully dense Y2SiO5 bulk material was achieved with a very high density of 99.7% theoretical.