A series of selected rare earth ions substituted bismuth silicates of the chemical formula Bi 4-x RE x (SiO 4 ) 3 (RE = La, Ce and Eu: X = 0.1, 0.2, 0.3) was synthesized by the solution method. Rietveld refinement study revealed that the compounds Bi 4 (SiO 4 ) 3 , Bi 3.9 La 0.1 (SiO 4 ) 3 , Bi 3.8 La 0.2 (SiO 4 ) 3 , Bi 3.7 La 0.3 (SiO 4 ) 3 , Bi 3.9 Ce 0.1 (SiO 4 ) 3 and Bi 3.9 Eu 0.1 (SiO 4 ) 3 were crystallized in cubic structure with I - 43d space group. Scanning electron microscopic images indicated that the larger and rod shaped particles were transformed into smaller and agglomerated ones when the rare earth ions were substituted for Bi ion in the octahedral site. UV–visible diffuse reflectance spectra displayed a shift in absorption edge upon rare earth ion substitution due to the overlapping of s-p transition band with Ln 3+ -O 2- charge transfer band. Bulk thermal expansion of the pure phases was tested using push rod dilatometer. The average coefficients of thermal expansion for Bi 4 (SiO 4 ) 3 , Bi 3.9 La 0.1 (SiO 4 ) 3 , Bi 3.9 Ce 0.1 (SiO 4 ) 3 and Bi 3.9 Eu 0.1 (SiO 4 ) 3 were found to be 5.19 x 10 −6 / ° C, 5.59 x 10 −6 / ° C, 7.10 x 10 −6 / ° C and 7.94 x 10 −6 / ° C, respectively. The effect of rare earth ionic substitution in thermal expansion behavior was investigated. • New rare earth substituted eulytite type ceramics were prepared by solution method. • Rietveld refinement study proved the formation of cubic phases with I - 43d space group. • The effect of rare earth ionic substitution was observed from SEM and UV-DRS. • Average thermal expansion coefficients the compounds were found to be in the range of 5.19–7.94 x 10 −6 /°C. • Heating and cooling cycles of thermal expansion showed different amounts of hysteresis.