Eu3+-activated red-emitting Ba2Gd2Si4O13 phosphors are prepared via microwave(MW) synthesis and solid-state(SS) method. The structural and luminescent properties of phosphors are investigated by X-ray diffraction(XRD), photoluminescence(PL) spectra and scanning electron microscopy(SEM). Upon 393 nm excitation, compared with the sample sintered by SS method, luminescence enhancement is observed in the sample synthesized by MW method. The mechanism of MW synthesis process is discussed in detail. Results indicate that the PL enhancement is probably related to the concave-convex phosphor surfaces and uniform grains, which may reinforce scattering of excitation light. Our research may further promote the understanding of MW synthesis and extend the application of Eu3+-activated Ba2Gd2Si4O13 in white light-emitting diodes.