采用高温固相法合成出正交相和三斜相结构的BiNbO4∶Eu3+样品，利用X 射线衍射(XRD)、拉曼光谱、吸收光谱和荧光光谱对样品的结构和光学性能进行了研究。结果表明: 900 ℃合成样品为正交相结构α-BiNbO4，而1 200 ℃得到三斜相结构β-BiNbO4。吸收光谱得到α相和β相BiNbO4的光学带隙分别为2.69 eV和2.96 eV，与第一性原理的理论结果2.640 eV和3.032 eV相吻合。Eu3+掺杂诱导二者的光学带隙蓝移至2.89 eV和3.05 eV，有效改变了其光响应范围。荧光光谱表明: Eu3+在两种结构的最强荧光峰均来自5D0→7F2电偶极跃迁，最强荧光峰分别位于615 nm和611 nm。Eu3+在β-BiNbO4中的荧光强度更高，而且其5D0→7F2和5D0→7F1的荧光强度比值更大。与Eu3+相似，Er3+在β-BiNbO4中具有更高的上转换荧光强度，其强度约是在α-BiNbO4中荧光的近40倍，说明三斜结构BiNbO4更适合做稀土离子的基质材料。

Orthorhombic phase α-BiNbO4∶Eu3+ and triclinic phase β-BiNbO4∶Eu3+ were synthesized by solid-state reaction method. Their structure and fluorescence properties were studied by X-ray diffractometer (XRD), Raman spectra, absorption spectra and luminescence spectra. Results indicate that pure α-BiNbO4 were successfully synthesized at 900 ℃, while triclinic phase β-BiNbO4 obtained at 1 200 ℃. The band structure of both structure BiNbO4 was studied using the first principle theory and absorption spectra. The optical band gap obtained for α-BiNbO4 and β-BiNbO4 are 2.69 eV and 2.96 eV respectively, in agreement with the theoretical result of 2.640 eV and 3.032 eV. After Eu3+ doping, theirs band gap blue shifts to 2.89 eV and 3.05 eV respectively, which effectively change their optical response range. The main emission peaks are from 5D0→7F2 transition of Eu3+ for both structural BiNbO4∶Eu, centerted at 615 nm and 611 nm respectively. But the emission intensity of β-BiNbO4∶Eu sample is much higher, and its luminescence intensity ratio between 5D0→7F2 and 5D0→7F1 transitions is much higher. For Er3+ doping, upconversion emission is observed for both structures excited at 980 nm. The upconversion emission intensity of β-BiNbO4∶Er sample is almost 40 times higher than that of α-BiNbO4∶Er sample. This results indicate that β-BiNbO4 is more suitable as the host material of rare earth ions doping phosphor.