The novel rare earth monosilicates (xRE1/x)2SiO5 (RE=Yb, Tm, Er, Y, Dy and Tb, x = 2–6) were prepared in order to establish the relationship between configurational entropy and lattice distortion, and the effect of configurational entropy on their properties was investigated. The results showed that the lattice distortion of (xRE1/x)2SiO5 increased gradually with the increase of configurational entropy, but the multi-principal component solid solution tended to form a highly symmetrical crystal structure when the configurational entropy was large enough, thus inhibiting the lattice distortion. (5RE1/5)2SiO5 had a maximum lattice distortion, which leaded to a relatively low thermal conductivity and coefficient of thermal expansion, and good CMAS corrosion resistance.