Uniform and well-crystallized octahedral NaGd(MoO4)(2):Eu3+ microcrystals have been successfully synthesized by a facile one-step hydrothermal synthesis method without involving any templates. The prepared samples were systematically characterized by powder X-ray diffraction, field-emission-scanning electron microscopy, photoluminescence (PL), and photoluminescent excitation spectra. The starting pH value played an important role in the pure-phase formation and uniform morphology of octahedral microcrystals. Detailed proofs indicated that the growth process of NaGd(MoO4)(2):Eu3+ microcrystals was dominated by a nucleation-crystallization-oriented attachment mechanism. Furthermore, the luminescent properties of the as-synthesized NaGd(MoO4)(2):Eu3+ microcrystals were investigated, demonstrating that the PL intensity was influenced by the different morphologies, and the bipyramidal octahedra NaGd(MoO4)(2):Eu3+ luminescent microcrystals might be applied as an excellent red component for near-UV white light emitting diodes. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3467792] All rights reserved.