A method comprising solution combustion followed by a heat treatment has been employed to synthesize cerium doped gadolinium pyrosilicate (Gd2Si2O7:Ce, or GPS:Ce) compounds. The powder obtained after the combustion was annealed at 1200 °C for 4 h and 1600°C for 3 h to synthesize triclinic and orthorhombic phases of the GPS, respectively. Structural and morphological characterizations of the synthesized compounds were carried out using X-ray diffraction and electron microscopy (SEM, TEM) techniques. A change in the enthalpy was observed in the differential thermal analysis data as a consequence of triclinic to orthorhombic phase transition in the GPS. Luminescence spectra and fluorescence decay time were measured at room temperature to characterize emission centers created in GPS compounds doped with trivalent rare earth ion (Ce3+). The triclinic GPS:Ce phase exhibited photoluminescence peaks at 379 nm and 410 nm while for the orthorhombic phase emissions at 353 nm and 380 nm were observed. A multi-component exponential decay pattern of the luminescence is observed for both the GPS:Ce phases. In addition, samples of the orthorhombic GPS:Ce were found to exhibit X-ray excited luminescence (XEL). © 2015 Elsevier B.V. All rights reserved.