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BaMoO4 with 3D hierarchical multilayer disc-like and nest-like architectures self-assembled from 2D nano-sheets were successfully synthesized via a microwave-assisted hydrothermal route without any surfactant.The as-prepared products were characterized by X-ray powder diffractometer (XRD),scanning electron microscope (SEM),field emission transmission electron microscope (FE-TEM) and photoluminescence (PL) spectrometer.The results show that the reaction parameters,including pH value,reactant concentration,and molar ratio of[Ba2+]/[MoO42-],played important roles on the morphologies of the final products.And the formation mechanism of 3D hierarchical architectures is a stepwise oriented aggregation-based self-assembly process.The superstructure characteristic of 3D nest-like BaMoO4 architecture was observed in HRTEM image and the corresponding Fast Fourier Transform (FFT) for the first time,and the superlattice reflections with non-integer indices occurred around the subcell reflections at±1/6(2a*+2c*).Room-temperature photoluminescence spectra of 3D BaMoO4 architectures reveal a strong and broad blue emission,and the 3D nest-like architectures own the enhanced intensity than multilayer discs.