Sr2SiO4 is an important inorganic host for lanthanide doped white light emitting diodes (LEDs). Strontium silicate (Sr2SiO4) samples doped with 1.0 mol% of Eu3+ and Dy3+ content were prepared via sol-gel route and characterized by X-ray diffraction (XRD), Raman spectroscopy and positron annihilation spectroscopy (PAS). The concentration of the dopant ion and the temperature of annealing were optimized for maximum luminescence intensity. The positron annihilation lifetime and coincidence Doppler broadening (CDB) measurements indicated that the local environment around the positron annihilation site is different in Eu+3 doped and Dy+3 doped samples. The results could be explained based on the different local site occupancy of Eu+3 and Dy+3 in the matrix.